EP2388146A2 - Druckverfahren, Verfahren zur Vorbereitung eines Aufdrucks, Verfahren zur Verarbeitung von Laminat, lichtemittierende härtbare Diodenbeschichtungszusammensetzung und lichtemittierende härtbare Diodentintenzusammensetzung - Google Patents

Druckverfahren, Verfahren zur Vorbereitung eines Aufdrucks, Verfahren zur Verarbeitung von Laminat, lichtemittierende härtbare Diodenbeschichtungszusammensetzung und lichtemittierende härtbare Diodentintenzusammensetzung Download PDF

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Publication number
EP2388146A2
EP2388146A2 EP20110166726 EP11166726A EP2388146A2 EP 2388146 A2 EP2388146 A2 EP 2388146A2 EP 20110166726 EP20110166726 EP 20110166726 EP 11166726 A EP11166726 A EP 11166726A EP 2388146 A2 EP2388146 A2 EP 2388146A2
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EP
European Patent Office
Prior art keywords
group
component
emitting diode
light
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20110166726
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English (en)
French (fr)
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EP2388146A3 (de
Inventor
Hiroyuki Suzuki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
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Fujifilm Corp
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Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of EP2388146A2 publication Critical patent/EP2388146A2/de
Publication of EP2388146A3 publication Critical patent/EP2388146A3/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/06—Lithographic printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0027—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers by lamination or by fusion of the coatings or layers

Definitions

  • the present invention relates to a printing method, a method for preparing an overprint, a method for processing a laminate, a light-emitting diode curable coating composition, and a light-emitting diode curable ink composition.
  • a printer for printing using an ultraviolet ray curable ink composition has been used, and it has been proposed to use one ultraviolet ray lamp (for example, a mercury lamp and the like) having a slightly longer dimension than the width of a body carrying a material to be printed by irradiating ultraviolet rays which cures an ultraviolet ray curable ink composition on a material to be printed (see, for example, JP2006-297690A ).
  • one ultraviolet ray lamp for example, a mercury lamp and the like
  • Such a lamp has a short lifespan as well as generating a large amount of heat and high power consumption, and accordingly in recent years, it has also been proposed to use a light-emitting diode which is capable of irradiating ultraviolet rays (see, for example, JP2009-208463A ).
  • the wavelength of the ultraviolet rays irradiated by a mercury lamp as described in JP2006-297690A is in a wide range of from 200 to 500 nm, whereas the wavelength of the ultraviolet rays irradiated by a light-emitting diode as described in JP2009-208463A has a very narrow range.
  • the printing method of the invention includes a printing step of printing an ink composition including (component A) a compound represented by the following formula. (I), (component B) a photopolymerization initiator, (component C) an ethylenically unsaturated compound, and (component D) a colorant on a material to be printed, and a curing step of irradiating ultraviolet rays having a peak wavelength at 375 to 395 nm by a a light-emitting diode to cure the printed ink composition.
  • component A a compound represented by the following formula. (I)
  • component B a photopolymerization initiator
  • component C an ethylenically unsaturated compound
  • component D a colorant on a material to be printed
  • X represents O, S, or NR
  • n represents an integer of 0 to 4
  • R represents a hydrogen atom, an allyl group, or an acyl group
  • R 1 to R 8 each independently represent a hydrogen atom or a monovalent substituent, two of R 1 to R 4 which are adjacent, respectively, may be bonded to each other to form a ring, and two of R 5 to R 8 which are adjacent, respectively, may be bonded to each other to form an aliphatic ring).
  • the printing method of the invention is preferably an offset printing method.
  • At least one of R 1 to R 8 in the formula (I) is preferably a halogen atom.
  • the component A is preferably a compound represented by the following formula (I-C).
  • R 1C to R 4C each independently represent a hydrogen atom or a halogen atom
  • R 5C to R 8C each independently represent a hydrogen atom or an alkyl group
  • at least one of R 1C to R 4C is a halogen atom
  • at least one of R 5C to R 8C is an alkyl group
  • the component B preferably includes an ⁇ -aminoketone-based compound and/or an acylphosphine oxide-based compound.
  • the component B preferably includes an ⁇ -aminoketone-based compound and an acylphosphine oxide-based compound.
  • the printing step is preferably a printing step of full-color printing using at least the ink composition on a material to be printed.
  • the method for preparing an overprint of the invention includes a coating step of coating a coating composition including (component A) a compound represented by the following formula (I), (component B) a photopolymerization initiator, and (component C) an ethylenically unsaturated compound on a printed matter, and a curing step of irradiating ultraviolet rays having a peak wavelength at 375 to 395 nm by a light-emitting diode to cure the coating composition thus coated.
  • a coating step of coating a coating composition including (component A) a compound represented by the following formula (I), (component B) a photopolymerization initiator, and (component C) an ethylenically unsaturated compound on a printed matter, and a curing step of irradiating ultraviolet rays having a peak wavelength at 375 to 395 nm by a light-emitting diode to cure the coating composition thus coated.
  • X represents O, S, or NR
  • n represents an integer of 0 to 4
  • R represents a hydrogen atom, an alkyl group, or an acyl group
  • R 1 to R 8 each independently represent a hydrogen atom or a monovalent substituent, two of R 1 to R 4 which are adjacent, respectively, may be bonded to each other to form a ring, and two of R 5 to R 8 which are adjacent, respectively, may be bonded to each other to form an aliphatic ring).
  • the method for processing a laminate of the invention includes a coating step of applying a coating composition including (component A) a compound represented by the following formula (I), (component. B) a photopolymerization initiator, and (component C) an ethylenically unsaturated compound on a printed matter, a laminating step of laminating a laminated film on the printed matter having the coating composition coated thereon, and a curing step of irradiating ultraviolet rays having a peak wavelength at 375 to 395 nm by a light-emitting diode to cure the coating composition thus coated.
  • a coating composition including (component A) a compound represented by the following formula (I), (component. B) a photopolymerization initiator, and (component C) an ethylenically unsaturated compound on a printed matter, a laminating step of laminating a laminated film on the printed matter having the coating composition coated thereon, and a curing step of ir
  • X represents O, S, or NR
  • n represents an integer of 0 to 4
  • R represents a hydrogen atom, an alkyl group, or an acyl group
  • R 1 to R 8 each independently represent a hydrogen atom or a monovalent substituent, two of R 1 to R 4 which are adjacent, respectively, may be bonded to each other to form a ring, and two of R 5 to R 8 which are adjacent, respectively, may be bonded to each other to form an aliphatic ring).
  • curable coating composition of the invention may include (component A) a compound represented by the following formula (I), (component B) a photopolymerization initiator, and (component C) an ethylenically unsaturated compound, and be cured by irradiation with a light-emitting, diode having a peak wavelength at 375 to 395 nm.
  • X represents O, S, or NR
  • n represents an integer of 0 to 4
  • R represents a hydrogen atom, an alkyl group, or an acyl group
  • R 1 to R 8 each independently represent a hydrogen atom or a monovalent substituent, two of R 1 to R 4 which are adjacent, respectively, may be bonded to each other to form a ring, and two of R 5 to R 8 which are adjacent, respectively, may be bonded to each other to form an aliphatic ring).
  • the component A is preferably a compound represented by the following formula (I-C).
  • R 1C to R 4c each independently represent a hydrogen atom or a halogen atom
  • R 5 to R 8 each independently represent a hydrogen atom or an alkyl group
  • at least one of R 1C to R 4C is a halogen atom
  • at least one of R 5C to R 8C is an alkyl group
  • the light-emitting diode curable coating composition of the invention is preferably a coating composition for offset printing.
  • the light-emitting diode curable ink composition of the invention may include (component A) a compound represented by the following formula (I), (component B) a photopolymerization initiator, (component C) an ethylenically unsaturated compound, and (component D) a colorant, and be cured by irradiation with a light-emitting diode having a peak wavelength at 375 to 395 nm.
  • component A a compound represented by the following formula (I)
  • component B a photopolymerization initiator
  • component C an ethylenically unsaturated compound
  • component D a colorant
  • X represents O, S, or NR n represents an integer of 0 to 4
  • R represents a hydrogen atom, an alkyl group, or an acyl group
  • R 1 to R 8 each independently represent a hydrogen atom or a monovalent substituent, two of R 1 to R 4 which are adjacent, respectively, may be bonded to each other to form a ring, and two of R 5 to R 8 which are adjacent, respectively, may be bonded to each other to form an aliphatic ring).
  • the component A is preferably a compound represented by the following formula (I-C).
  • R 1C to R 4C each independently represent a hydrogen atom or a halogen atom
  • R 5C to R 8C each independently represent a hydrogen atom or an alkyl group
  • at least one of R 1C to R 4C is a halogen atom
  • at least one of R 5C to R 8C is an alkyl group
  • the light-emitting diode curable ink composition of the invention is preferably a curable ink composition for offset printing.
  • a light-emitting diode curable ink composition which provides a cured matter having excellent non-tackiness and hue can be provided.
  • a light-emitting diode curable coating composition which provides a cured matter having excellent non-tackiness and transparency can be provided.
  • a printing method, a method for preparing an overprint, and a method for processing a laminate, each of which uses the ink composition or the coating composition can be provided.
  • Fig. 1 is a view showing an absorption spectrum of the compound (1-14), diethylthioxanthone, and IRGACURE 907.
  • Fig. 2 is a schematic structural view showing the printer which can be used in one embodiment of the printing method of the invention.
  • Fig. 3(a) is a perspective view showing the arrangements of the impression cylinder and the light-emitting diode in the ultraviolet ray-irradiated portion T
  • Fig. 3(b) is a front view of a substrate equipped with a light-emitting diode in the ultraviolet ray-irradiated portion T.
  • Fig. 4 is an overall structural view of a coating device used in one embodiment of the method for processing a laminate of the invention.
  • Fig. 5 is an overall structural view of another coating device used in one embodiment of the method for processing a laminate of the invention.
  • the light-emitting diode curable coating composition of the invention may include (component A) a compound represented by the following formula (I), (component B) a photopolymerization initiator, and (component C) an ethylenically unsaturated compound.
  • X represents O, S, or NR
  • n represents an integer of 0 to 4
  • R represents a hydrogen atom, an alkyl group, or an acyl group
  • R 1 to R 8 each independently represent a hydrogen atom or a monovalent substituent, two of R 1 to R 4 which are adjacent, respectively, may be bonded to each other to form a ring, and two of R 5 to R 8 which are adjacent, respectively, may be bonded to each other to form an aliphatic ring).
  • the light-emitting diode curable ink composition of the invention may include (components A) a compound represented by the formula (I), (component B) a photopolymerization initiator, (component C) an ethylenically unsaturated compound, and (component D) a colorant.
  • both of the coating composition of the invention and the ink composition of the invention may also be simply referred to as the "curable composition”.
  • the "light-emitting diode curable” or “curable” refers to being cured by irradiation with a light-emitting diode having a light-emitting peak wavelength at 375 to 395 nm, and preferably irradiation for 0.1 to 10 seconds.
  • the printing method of the invention may include a printing step of printing an ink composition including (component A) a compound represented by the formula (I), (component B) a photopolymerization initiator, (component C) an ethylenically unsaturated compound, and (component D) a colorant (the ink composition of the invention) on a material to be printed, and a curing step of irradiating ultraviolet rays having a peak wavelength at 375 to 395 nm by a light-emitting diode to cure the printed ink composition.
  • component A a compound represented by the formula (I)
  • component B a photopolymerization initiator
  • component C an ethylenically unsaturated compound
  • component D a colorant
  • the method for preparing an overprint of the invention may include a coating step of coating a coating composition including (component A) a compound represented by the following formula (I), (component B) a photopolymerization initiator, and (component C) an ethylenically unsaturated compound (the coating composition of the invention) on a printed matter, and a curing step of irradiating ultraviolet rays having a peak wavelength at 375 to 395 nm by a light-emitting diode to cure the coating composition thus coated.
  • the method for processing a laminate of the invention may include a coating step of coating a coating composition including (component A) a compound represented by the following formula (I), (component B) a photopolymerization initiator, and (component C) an ethylenically unsaturated compound (the coating composition of the invention) on a printed matter, a lamination step of laminating a laminate film on the printed matter having the coating composition coated thereon, and a curing step of irradiating ultraviolet rays having a peak wavelength at 375 to 395 nm by a light-emitting diode to cure the coating composition thus coated.
  • a coating step of coating a coating composition including (component A) a compound represented by the following formula (I), (component B) a photopolymerization initiator, and (component C) an ethylenically unsaturated compound (the coating composition of the invention) on a printed matter, a lamination step of laminating a laminate film on the printed matter having
  • the light-emitting diode curable coating composition of the invention can be used in a composition used for UV ink, or UV varnish for an overprint, a three-dimensional structure, or the like, a composition for processing a laminate, or the like.
  • the cured composition does not substantially have unnecessary light absorption (yellowing) in a visible region, which is thus advantageous.
  • the light-emitting diode curable coating composition of the invention preferably has no colorant, and preferably, it has substantially no absorption in the visible region.
  • the expression "having substantially no absorption in the visible region” means either having no absorption in a visible region of 400 to 700 nm or having only a level of absorption in the visible region that does not cause any problems as a photocurable coating composition.
  • a 5 ⁇ m optical path length transmittance of the coating composition in a wavelength range of 400 to 700 nm is at least 70%, preferably at least 80%, and particularly preferably at least 90% on average.
  • the light-emitting diode curable ink composition of the invention is a colored ink composition and contains a colorant.
  • the light-emitting diode curable ink composition of the invention can be suitably used as an ink composition for relief printing, lithographic printing, intaglio printing, and stencil printing, such as flexographic printing, offset printing, gravure printing, screen printing, and the like.
  • the curable composition of the invention may include a compound represented by the following formula (I) in order to promote the polymerization-initiating ability of the photopolymerization initiator by irradiation with a light-emitting diode having a light-emitting peak wavelength at 375 to 395 nm.
  • the compound represented by the formula (I) functions as a sensitizer in the curable composition of the invention.
  • X represents O, S, or NR
  • n represents an integer of 0 to 4
  • R represents a hydrogen atom, an alkyl group, or an acyl group
  • R 1 to R 8 each independently represent a hydrogen atom or a monovalent substituent, two of R 1 to R 4 which are adjacent, respectively, may be bonded to each other to for a ring, and two of R 5 to R 8 which are adjacent, respectively, may be bonded to each other to form an aliphatic ring).
  • X represents O, S, or NR
  • R represents a hydrogen atom, an alkyl group, or an acyl group.
  • n represents an integer of 0 to 4.
  • X is preferably O or S, and more preferably S.
  • n when n is 0, there is no carbon, atom to which R 7 and R 8 are bonded, and X which contains a hetero atom and the carbon atom to which R 5 and R 6 are bonded are directly bonded to each other to form an X-containing 5-membered hetero ring.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 each independently represent a hydrogen atom or a monovalent substituent. Further, examples of the substituent in the invention include atoms and atom groups.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 represent a monovalent substituent
  • examples of the monovalent substituent include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an amino group, a mono or dialkylamino group, an alkoxy group, an aryloxy group, an amide group, an arylamino group, an ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, a hetero ring oxy group, an azo group, an acyloxy group,
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 in the formula (I) represent a monovalent substituent
  • preferred examples of the alkyl group include those having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group.
  • alkoxy group examples include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an n-butosy group, an isobutoxy group, a sec-butoxy group, and a t-butoxy group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R 1 , R 2 , R 3 , and R 4 which are adjacent, respectively, may be bonded to each other, for example, condensed, to form a ring.
  • the ring structure When they form a ring, the ring structure may be a 5- or 6-membered aliphatic ring, aromatic ring, or the like, or may be a hetero ring containing an element other than a carbon atom.
  • R 5 , R 6 , R 7 , and R 8 which are adjacent, respectively, may be bonded to each other to form an aliphatic ring, but does not form an aromatic ring. Also, when they form the aliphatic ring, R 5 and R 7 are preferably bonded to each other to form an aliphatic ring.
  • the rings thus formed may further be combined to form a polycyclic condensed ring or a spiro ring.
  • these ring structures may further have a substituent such as each of those cited as examples for the monovalent substituents represented by R 1 to R 8 in the formula (I).
  • Examples of the hetero atom when the ring structure thus formed is a hetero ring include N, O, and S.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 is preferably a monovalent substituent.
  • the compound represented by the formula (I) is preferably a compound represented by the following formula (I-A).
  • R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A , and R 8A each independently represent a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, a cyano group, a nitro group, all amino group, an alkylthio group, a mono- or dialkylamino group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an acyl group, a carboxylic group, or a sulfo group.
  • two of R 1A , R 2A , R 3A , and R 4A which are adjacent, respectively, may be bonded to (condensed with) each other to form a ring.
  • R 1A , R 2A , R 3A , and R 4A which are adjacent, respectively, are bonded to (condensed with) each other, they may form a 5- or 6-membered aliphatic ring or aromatic ring, and these rings may be hetero rings containing an element other than a carbon atom, and the rings thus formed may further be combined to form a polycyclic condensed ring or a spiro ring.
  • these ring structures may further have a substituent such as each of those cited as examples for the monovalent substituent represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 in the formula (I).
  • Examples of the hetero atom when the ring structure is a hetero ring include N, O, and S.
  • the compound represented by the formula (I) is more preferably a compound represented by the following formula (I-B).
  • R 1B , R 2B , R 3B , R 4B , R 5B , R 6B , R 7B , and R 8B each independently represent a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, a cyano group, a nitro group, an amino group, an alkylthio group, a mono- or dialkylamino group, an alkoxy, group, an alkoxycarbonyl group, an acyloxy group, an acyl group, a carboxylic group, or a sulfo group.
  • two of R 1B , R 2B , R 3B , and R 4B which are adjacent, respectively, may be bonded to (condensed with) each other to form a ring.
  • R 1B , R 2B , R 3B , and R 4B which are adjacent, respectively, are bonded to (condensed with) each other, they may form a 5- or 6-membered aliphatic ring or aromatic ring, and these rings may be hetero rings containing an element other than a carbon atom, and the rings thus formed may further be combined to form a polycyclic condensed ring or a spiro ring.
  • these ring structures may further have a substituent such as each of those cited as examples for the monovalent substituent represented by R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , and R 8 in the formula (I).
  • Examples of the hetero atom when the ring structure is a hetero ring include N, O, and S.
  • the compound represented by the formula (I) is even more preferably a compound represented by the following formula (I-C).
  • R 1C to R 4C each independently represent a hydrogen atom or a halogen atom
  • R 5C to R 8C each independently represent a hydrogen atom or an alkyl group
  • at least one of R 1C to R 4C is a halogen atom
  • at least one of R 5C to R 8C is an alkyl group.
  • the number of carbon atoms of the alkyl group is preferably 1 to 8, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 1.
  • halogen atom is preferably a chlorine atom.
  • Fig. 1 the vertical axis of Fig. 1 denotes a molar absorbance coefficient ⁇ (mol -1 ⁇ L ⁇ cm -1 ) and the horizontal axis denotes a wavelength (nm).
  • the molar absorbance coefficient of the compound As for the molar absorbance coefficient of the compound, a 0.01 g/L solution of a compound to be measured in methanol was produced and the absorbance was measured using cary-5uv-vis-NIRSPECTROPHOTMETERS manufactured by Varian Inc. Further, the molar absorbance coefficients ⁇ (mol -1 ⁇ L ⁇ cm -1 ) at 365 nm and 400 nm were calculated.
  • Sensitizer ⁇ at 365 nm ⁇ at 400 nm Compound (I-14) 2,578 156 Diethylthioxanthone 3,792 4,078 Benzophenone 81 0 N-Ethylcarbazole 92 0
  • the method for synthesizing the compound represented by the formula (I) is not particularly limited, but a known method can be used, and thus, the compound can be synthesized according to the method described in, for example, JP2004-189695A , " Tetrahedron", Vol. 49, p. 939 (1993 ), “ Journal of Organic Chemistry", p. 893 (1945 ), and “ Journal of Organic Chemistry", p. 4939 (1965 ), or the like.
  • the content of the compound represented by the formula (I) in the curable composition of the invention is preferably on the order of 0.05 to 40% by weight, more preferably 0.1 to 30% by weight, and even more preferably 0.2 to 25% by weight, based on the solid content of the coating composition.
  • the compound represented by the formula (I) has hardly any adsorption in the visible light region, even if an amount such that an effect can be exhibited is added, there is an advantage that there is no probability of affecting the hue of the curable composition, which is an advantage.
  • the content in the curable composition of the invention is an amount that satisfies the ratio by weight of the photopolymerization initiator:the compound represented by the formula (I) of preferably 200: 1 to 1:200, more preferably 50:1 to 1: 50, and even more preferably 20:1 to 1:5.
  • the sensitizer absorbs a specific actinic radiation and attains an electronically excited state.
  • the sensitizer in the electronically excited state causes actions such as electron transfer, energy transfer, heat generation, and the like upon contact with the photopolymerization initiator.
  • a known sensitizer in addition to the compound represented by the formula (I), a known sensitizer can be used in combination therewith as long as the effects of the invention are not impaired.
  • the amount of the other sensitizer used is preferably 1:5 to 100:1, more preferably 1:1 to 100:1, and even more preferably 2:1 to 100:1 of the compound represented by the formula (I):the other sensitizer ratio by weight, based on the compound represented by the formula (I).
  • Examples of the known sensitizer that can be used in combination include benzophenone, thioxanthone, isopropylthioxanthone, anthraquinone, 3-acylcoumarin derivatives, terphenyl, styryl ketone, 2-(aroylmethylene)thiazoline camphorquinone, eosin, rhodamine, erythrosine, and the like.
  • sensitizer that can be used in combination are as follows.
  • thioxanthone 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxycarbonylthioxanthone, 2-ethoxycarbonylthioxanthone, 3-(2-methoxyethoxycarbonyl)thioxanthone, 4-butoxycarbonylthioxanthone, 3-butoxycarbonyl-7-methylthioxanthone, 1-cyano-3-chlorothioxanthone, 1-ethoxycarbonyl- 3-chlorothioxanthone, 1-ethoxycarbonyl-3-ethoxythioxanthone, 1-ethoxycarbonyl-3-aminothioxanthone, 1-ethoxycarbonyl-3-phenylsulfurylthioxanthone, 3,4-di-[2-(
  • acetophenone 3-methoxyacetophenone, 4-phenylacetophenone, benzil, 2-acetylnaphthalene, 2-naphthaldehyde, 9,10-naphthoquinone, 9-fluorenone, dibenzosuberone, xanthone, 2,5-bis(4-diethylaminobenzylidene)cyclopentanone, an ⁇ -(para-dimethylaminobenzylidene) ketone such as, for example, 2-(4-dimethylaminobenzylidene)indan-1-one or 3-(4-dimethylaminophenyl)-1-mdan-5-ylpropenone, 3-phenylthiophthalimide, N-methyl-3,5-di(ethylthio)phthalimide.
  • sensitizers used in the photopolymerizable compositions described in JP2009-221441A , JP2005-36152A , or the like can be used in combination therewith in the curable composition of the invention.
  • the curable composition of the invention contains a photopolymerization initiator.
  • photopolymerization initiator a known polymerization initiator can be used.
  • a radical photopolymerization initiator is preferably used.
  • the photopolymerization initiator used in the curable composition of the invention is a compound that absorbs actinic radiation and generates a polymerization initiating species.
  • the actinic radiation used for initiating the polymerization include ⁇ -rays, ⁇ -rays, an electron beam, ultraviolet rays, visible light, and infrared rays.
  • the wavelength used is not particularly limited, but is preferably a wavelength range of 200 to 500 nm, and more preferably a wavelength range of 200 to 450 nm.
  • Preferred examples of the radical photopolymerization initiator that can be used in the invention include (a) aromatic ketones, (b) acylphosphine compounds, (c) aromatic onium salt compounds, (d) organic peroxides, (e) thio compounds, (f) hexaarylbiimidazole compounds, (g) ketoxime ester compounds, (h) borate compounds, (i) azinium compounds, (j) metallocene compounds, (k) active ester compounds, (1) compounds having carbon-halogen bonds, (m) azo-based compounds, and the like.
  • Preferred examples of the (a) aromatic ketones that are used in the invention include a compound having a benzophenone skeleton or a thioxanthone skeleton described in " RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY" J. P. Fouassier, J. F. Rabek (1993), p. 77-117 .
  • the compounds described below can be cited.
  • particularly preferred examples of the (a) aromatic ketones include the following compounds.
  • a benzoin derivative described in JP-S47-23664B , an aroylphosphonic acid ester described in JP-S57-30704A , a dialkoxybenzophenone described in JP-S60-26483B , for example, a compound described below can be cited.
  • a thio-substituted aromatic ketone described in JP-S61-194062A for example, a compound described below can be cited.
  • An ⁇ -aminoketone-based compound and/or an acylphosphine oxide-based compound is particularly preferred.
  • the ⁇ -aminoketone-based compound is preferably the compound represented by the following formula (1).
  • Ar is a phenyl group substituted with -SR 13 or -N(R 7 )(R 8 ), wherein R 13 represents a hydrogen atom or an alkyl group.
  • R 1 and R 2 each represents an alkyl group having 1 to 8 carbon atoms.
  • R 1 and R 2 may be bonded to each other to form an alkylene group having 2 to 9 carbon atoms.
  • R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 2 to 4 carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 3 to 5 carbon atoms.
  • R 3 and R 4 may be bonded to each other to form an alkylene group having 3 to 7 carbon atoms, the alkylene group may contain -O- or -N(R 12 )- in the alkylene chain, wherein R 12 represents an alkyl group having 1 to 4 carbon atoms.
  • R 7 and R 8 independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 2 to 4 carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 3 to 5 carbon atoms.
  • R 7 and R 8 may be bonded to each other to form an alkylene group having 3 to 7 carbon atoms, and the alkylene group may contain -O- or -N(R 12 )- in the alkylene chain.
  • R 12 has the same meaning as above.
  • Examples of the compounds encompassed by the ⁇ -ammoketones include 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1-(4-hexylphenyl)-2-morpholmopropan-1-one, 2-ethyl-2-dimethylammo-1-(4-morpholinophenyl)-butan-1-one, and the like. Furthermore, there are commercially available products such as the IRGACURE series manufactured by Nihon Ciba-Geigy K. K., for example, IRGACURE 907, IRGACURE 379, and the like, which are also included in the compounds encompassed by the ⁇ -aminoketones and can be used suitably in the invention.
  • the acylphosphine oxide-based compound is preferably a compound represented by the following formula (2) or (3).
  • R 5 and R 6 each independently represent an aliphatic group, an aromatic group, an aliphatic oxy group, an aromatic oxy group, or a heterocyclic group
  • R 7 represents an aliphatic group, an aromatic group, or a heterocyclic group.
  • Examples of the aliphatic group in R 5 , R 6 , or R 7 include an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkenyl group, a substituted alkynyl group, an aralkyl group, a substituted aralkyl group, and the like, and among these, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group, and a substituted aralkyl group are preferred, and an alkyl group and a substituted alkyl group are particularly preferred.
  • the aliphatic group may be a cyclic aliphatic group or an open-chain aliphatic group. The open-chain aliphatic group may be branched.
  • alkyl group examples include straight-chained, branched, and cyclic alkyl groups, and the number of carbon atoms of the alkyl group is preferably 1 to 30, and more preferably 1 to 20. A preferred number of carbon atoms for the alkyl moiety of the substituted alkyl group is the same as that for the alkyl group. Also, the alkyl group may be either a substituted alkyl group or an unsubstituted alkyl group.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, an octadecyl group, a cyclohexyl group, a cyclopentyl group, a neopentyl group, an isopropyl group, an isobutyl group, and the like.
  • Examples of a substituent of the substituted alkyl group include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, or a bromine atom), a hydroxy group, an alkoxycarbonyl group having no more than 30 carbon atoms (for example, a methoxycarbonyl group, an ethoxycarbonyl group, and a benzyloxycarbonyl group), an alkylsulfonylaminocarbonyl group having no more than 30 carbon atoms, an arylsulfonylaminocarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an acylaminosulfonyl group having no more than 30 carbon atoms, an alkoxy group having no more than 30 carbon atoms (for example, a methoxy group, an ethoxy group, a
  • the carboxyl group, the sulfo group, the hydroxy group, and the phosphono group may be in salt form.
  • a cation forming the salt preferred examples thereof include an organic cation (for example, primary to quaternary ammonium), a transition metal coordination complex cation (a compound described in JP2791143 , and the like), and a metal cation (for example, Na + , K + , Li + , Ag + , Fe 2+ , Fe 3+ , Cu + , Cu 2+ , Zn 2+ , Al 3+ , and the like).
  • alkenyl group examples include straight-chained, branched, or cyclic alkenyl groups, and the number of carbon atoms of the alkenyl group is preferably 2 to 30, and more preferably 2 to 20.
  • the alkenyl group may be either a substituent-containing substituted alkenyl group or an unsubstituted alkenyl group, and a preferred range for the number of carbon atoms of the alkenyl moiety of the substituted alkenyl group is the same as for the alkenyl group.
  • Examples of the substituent of the substituted alkenyl group include the same substituents as for the substituted alkyl group, and an aryl group having no more than 30 carbon atoms (for example, a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, an ⁇ -naphthyl group, and the like).
  • alkynyl group examples include straight-chained, branched, or cyclic alkynyl groups, and the number of carbon atoms of the alkynyl group is preferably 2 to 30, and more preferably 2 to 20.
  • the alkynyl group may be either a substituent-containing substituted alkynyl group or an unsubstituted alkynyl group, and a preferred range for the number of carbon atoms of the alkynyl moiety of the substituted alkynyl group is the same as for the alkynyl group.
  • substituent of the substituted alkynyl group examples include the same substituents as for the alkenyl group.
  • the aralkyl group examples include straight-chained, branched, or cyclic aralkyl groups, and the number of carbon atoms of the aralkyl group is preferably 7 to 35, and more preferably 7 to 25. Furthermore, the aralkyl group may be either a substituent-containing substituted aralkyl group or an unsubstituted aralkyl group, and a preferred range for the number of carbon atoms of the aralkyl moiety of the substituted aralkyl group is the same as for the aralkyl group. Examples of the substituent of the substituted aralkyl group include the same substituents as for the alkenyl group.
  • Examples of the aromatic group represented by R 5 , R 6 , or R 7 include an aryl group and a substituted aryl group.
  • the number of carbon atoms of the aryl group is preferably 6 to 30, and more preferably 6 to 20.
  • a preferred range for the number of carbon atoms of the aryl moiety of the substituted aryl group is the same as for the aryl group.
  • Examples of the aryl group include a phenyl group, an ⁇ -naphthyl group, a ⁇ -naphthyl group, and the like.
  • Examples of a substituent of the substituted aryl group include the same substituents as for the alkenyl group.
  • Examples of the aliphatic oxy group represented by R 5 or R 6 include a substituted or unsubstituted alkoxy group, an alkenyloxy group, an group, an aralkyloxy group, and the like, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms is preferred, and examples thereof include a methoxy group, an ethoxy group, a butoxy group, an octyloxy group, a phenoxyethoxy group, and the like.
  • the aliphatic oxy group is not limited thereto.
  • Examples of the aromatic oxy group represented by R 5 or R 6 include a substituted or unsubstituted aryloxy group; a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms is preferred, and examples thereof include a phenoxy group, a methylphenyloxy group, a chlorophenyloxy group, a methoxyphenyloxy group, an octyloxyphenyloxy group, and the like.
  • the aromatic oxy group is not limited thereto.
  • Preferred examples of the heterocyclic group represented by R 5 , R 6 , or R 7 include N, O, or S atom-containing heterocyclic groups, and examples thereof include a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrrolyl group, and the like.
  • the compound represented by the formula (2) may be bonded, via R 5 , R 6 , or R 7 , to another compound represented by the formula (2) to thus form a multimer having 2 or more acylphosphine structures.
  • R 8 and R 10 in the formula (3) each independently represent an alkyl group, an aryl group, or a heterocyclic group
  • R 9 represents an alkyl group, an aryl groups, an alkoxy group, an aryloxy group, or a heterocyclic group.
  • the alkyl group, the aryl group, the heterocyclic group, the alkoxy group, and the aryloxy group represented by R 8 , R 9 , or R 10 may have a substituent, and examples of the substituent include the same substituents as for the formula (2).
  • the alkyl group, the aryl group, the heterocyclic group, the alkoxy group, and the aryloxy group in the formula (3) have the same meanings as for the formula (2) above.
  • the compound represented by the formula (3) may be bonded, via R 8 , R 9 , or R 10 to another compound represented by the formula (3) to form a multimer having 2 or more acylphosphine structures.
  • examples of the acylphosphine oxide-based compound represented by the formula (2) or (3) include the compounds described in JP-563-407998 , JP-H05-29234B , JP-H10-95788A , JP-H10-29997A , or the like.
  • acylphosphine oxide-based compound examples include the compound described below (exemplified Compounds (P-1) to (P-26)), but in the invention, the acylphosphine oxide-based compound is not limited thereto.
  • Preferred examples of the (c) aromatic onium salt compound used as a radical initiator in the invention include the compounds represented by the following formulae (1) to (3).
  • Ar 1 and Ar 2 each independently represent an aryl group having not more than 20 carbon atoms, which may have a substituent.
  • Preferred examples of the substituents when the aryl group has a substituent include a halogen atom, a nitro group, an alkyl group having not more than 12 carbon atoms, an alkoxy group having not more than 12 carbon atoms, or an aryoxyl group having not more than 12 carbon atoms.
  • (Z 2 ) - represents a counter ion selected from the group consisting of a halide ion, a perchlorate ion, a carboxylate ion, tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, and preferred examples thereof include a perchlorate ion, a hexafluorophosphate ion, and an arylsulfonate ion.
  • Ar 3 represents an aryl group having not more than 20 carbon atoms, which may have a substituent.
  • Preferred examples of the substituent include a halogen atom, a nitre group, an alkyl group having not more than 12 carbon atoms, an alkoxy group having not more than 12 carbon atoms, an aryoxyl group having not more than 12 carbon atoms, an alkylamino group having not more than 12 carbon atoms, a dialkylamino group having not more than 12 carbon atoms, an arylamino group having not more than 12 carbon atoms, or a diaryl group having not more than 12 carbon atoms.
  • (Z 3 ) - represents a counter ion having the same meaning as defined for (Z 2 ) - .
  • R 23 , R 24 , and R 25 may be the same as or different from each other and represent a hydrocarbon group having not more than 20 carbon atoms, which may have a substituent Preferred examples of the substituent include a halogen atom, a nitro group, an alkyl group having not more than 12 carbon atoms, an alkoxy group having not more than 12 carbon atoms, or an aryoxyl group having not more than 12 carbon atoms.
  • (Z 4 ) - represents a counter ion having the same meaning as defined for (Z 2 ) - .
  • the onium salt used in the invention preferably has a maximum absorption wavelength of 400 nm or less, and more preferably 360 nm or less.
  • the handling can be performed under a white light lamp,
  • Preferred examples of the (d) organic peroxide which is used as the radical initiator in the invention include almost all organic compounds having at least one oxygen-oxygen bond in the molecules thereof which include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyelohexanone peroxide, acetylacetone peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, tert-butylhydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramethane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydro
  • peroxy ester compounds such as 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-amylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxy-carbonyl)benzophenone, 3,3',4,4'-tetra(tert-octylpetoxycarbonyl)benzophenone, 3,3',4,4'-tetra(cumylperxoxycarbonyl)benzophenone, 3,3',4,4'-tetra(p-isopropylcumylperoxycarbonyl)benzophenone, di-tert-butyldiperoxy isophthalate, and the like are preferred.
  • Examples of the (e) thio compound which is preferred as the radical initiator used in the invention include compounds having a structure represented by the following formula (4):
  • R 26 represents an alkyl group, an aryl group or a substituted aryl group.
  • R 27 represents a hydrogen atom or an alkyl group.
  • R 26 and R 27 represent non-metallic atomic groups necessary for being combined with each other to form a 5- to 7-membered ring which may contain a hetero atom selected from an oxygen atom, a sulfur atom, and a nitrogen atom).
  • the alkyl group in the formula (4) preferably has 1 to 4 carbon atoms.
  • the aryl group is preferably one having 6 to 10 carbon atoms, such as a phenyl group and a naphthyl group, and examples of the substituted aryl group include the above-described aryl groups substituted with a halogen atom such as a chlorine atom, an alkyl group such as a methyl group, or an alkoxy group such as a methoxy group and an methoxy group.
  • R 27 is preferably an alkyl group having 1 to 4 carbon atom.
  • Specific examples of the thio compound represented by the formula (4) include the following compounds.
  • Preferred examples of the (f) hexaarylbiimidazole compound as the radical initiator which is used in the invention include lophine dimers described in JP-S45-03737713 and JP-S44-086516B , for example, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbimidazole, 2,2-bis(o-bromophenyl)-4,4',3,3'-tetraphenylbiimidazole, 2,2' -bis(o,p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(m-methoxyphenyl) biimidazole, 2,2'-bis(o,o'-dichlorophenyl)-4,4',5,5'-tetrapheny
  • Examples of the (g) ketoxime ester compound which is preferred as the radical initiator used in the invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 3-acestoxyiminopentan-3-one, 2-acetoxylmino-1-phenylpropan- 1-one, 2-benzoylosyimino-1-phenylpropan- 1-one, 3-p-toluenesulfonyloxyiminobutan-2-one, 2'ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.
  • Examples of the (h) borate compound which is preferred as the radical initiator used in the invention include a compound represented by the following formula (5).
  • R 28 , R 29 , R 30 , and R 31 may be the same as or different from each other and each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted heterocyclic group, or at least two of R 28 R 29 , R 30 , and R 31 may be combined with each other to form a cyclic structure, provided that at least one of R 28 , R 29 , R 30 , and R 31 represents a substituted or unsubstituted alkyl group.
  • (Z 5 ) + represents an alkali metal cation or a quaternary ammonium cation).
  • the alkyl groups of R 28 to R 31 include straight-chain, branched, and cyclic alkyl groups, and those having 1 to 18 carbon atoms are preferred. Specific examples thereof include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
  • substituted alkyl groups include the above-described alkyl group containing, as a substituent, a halogen atom (for example, -Cl, -Br, and the like), a cyano group, a nitro group, an aryl group (preferably a phenyl group), a hydroxy group, -COOR 32 (wherein R 32 represents a hydrogen atom or an alkyl or aryl group having 1 to 14 carbon atoms), -OCOR 33 , or -OR 34 (wherein R 33 and R 34 represent an alkyl or aryl group having 1 to 14 carbon atoms), and a group represented by the following formula.
  • a halogen atom for example, -Cl, -Br, and the like
  • a cyano group for example, -Cl, -Br, and the like
  • R 32 represents a hydrogen atom or an alkyl or aryl group having 1 to 14 carbon atoms
  • -OCOR 33 or
  • R 35 and R 36 each independently represent a hydrogen atom, or an alkyl or aryl group having 1 to 14 carbon atoms).
  • the aryl groups of R 28 to R 31 above include monocyclic to tricyclic aryl groups such as a phenyl group, a naphthyl group, and the like, and the substituted aryl groups include the aryl groups above that have additionally the substituent group for the substituted alkyl group described above or an alkyl group having 1 to 14 carbon atoms.
  • the alkenyl groups of R 28 to R 31 include straight-chain, branched and cyclic alkenyl groups having 2 to 18 carbon atoms, and the substituent groups of the substituted alkynyl group include those described as the substituent groups of the substituted alkyl group.
  • the alkynyl groups of R 28 to R 31 include straight-chain or branched-chain alkynyl groups having 2 to 28 carbon atoms, and the substituent groups of the substituted alkynyl group include those described as the substituent groups of the substituted alkyl group.
  • the heterocyclic groups of R 28 to R 31 include heterocyclic groups of 5- or higher membered rings, preferably 5- to 7-membered rings, containing at least one of N, S, and O atoms, and the heterocyclic group may be a fused ring.
  • the heterocyclic groups may have additionally one of the groups described as the substituent groups of the substituted aryl group described above as their substituent group.
  • Specific examples of the compounds represented by Formula (5) include the compounds described in U.S. Pat. Nos. 3,567,453 and 4,343,891 , and E.P. Nos. 109772 and 109773 , and the compounds described below.
  • Examples of the (i) azinium compound which is preferred as the radical initiator used in the invention include compounds having N-O bonds described in JP-S63-138345A , JP-S63-142345A , JP-S63-142346A , JP-S63-143537A , and JP-S46-042363B .
  • Examples of the (i) metallocene compound which is preferred as the radical initiator used in the invention include titanocene compounds described in JP-S59-152396A , JP-S61-15197A , JP-S63-41484A , JP-H02-000249A , and JP-H02-004705A , and iron-arene complexes described in JP-H01-304453A and JP-H01-152109A .
  • titanocene compound examples include dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, dicyelopetitadienyl-Ti-2,6-difuorophen-1-yl, dicyclopentadienyl-Ti-bis-2,4-diflurophen-1-yl, dimethylcyctopcntadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,
  • Preferred examples of the (k) active ester compound which is preferred as the radical initiator used in the invention include imidosulfonate compounds described in JP-S6 2-006223B , and active sulfonates described in JP-S63-14340B and JP-S59-174831A .
  • Examples of the (1) compound having a carbon-halogen bond which is preferred as the radical initiator used in the invention include the compounds represented by the following formulae (6) to (12):
  • X 2 represents a halogen, atom
  • Y 1 represents -C(X 2 ) 3 , -NH 2 , -NHR 38 , -NR 38 , or -OR 38
  • R 38 represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group
  • R 37 represents -C(X 2 ) 3 , an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group).
  • R 39 represents an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxyl group, a nitro group or a cyano group
  • X 3 represents a halogen atom
  • n represents an integer of 1 to 3
  • R 42 and R 43 represent an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group, and R 44 has the same meaning as defined for R 38 in the formula (6)).
  • R 45 represents an aryl group or heterocyclic group, which may be substituted.
  • R 46 represents a trihaloalkyl group or trihaloalkenyl group having 1 to 3 carbon atoms, and p represents 1, 2, or 3).
  • L 7 represents a hydrogen atom or a group represented by the formula -CO-(R 47 )q(C(X 4 ) 3 ) r
  • Q 2 represents a sulfur atom, a selenium atom, an oxygen atom, a dialkylmelhylene group, an alken-1,2-ylene group, a 1.2-phenylene group or -N-R
  • M 4 represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group or a 1,2-arylene group
  • R 48 represents an alkyl group, an aralkyl group or an alkoxyalkyl group
  • R 47 represents a divalent carbocyclic or heterocyclic aromatic group
  • X 5 represents a halogen atom
  • t represents an integer of 1 to 3
  • s represents an integer of 1 to 4
  • R 49 represents a hydrogen atom or -CH( 3-t )X 5 t
  • R 50 represents an s-valent unsaturated organic group, which may be substituted).
  • X 6 represents a halogen atom
  • v represents an integer of 1 to 3
  • u represents an integer of 1 to 4
  • R 51 represents a hydrogen atom or CH (3-v) X 6 v
  • R 52 represents a u-valent unsaturated organic group, which may be substituted).
  • the compound having a carbon-halogen bond include the compounds described by Wakabayashi et al. in Bull. Chem. Soe. Japan, 42, 2924 (1969 ), for example, 2-Phenyl-4,5-bis(trichlorothyl)-s-triazine, 2-(p-chloropheiiyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dichlorophenyl)-4,6-bis(thchloromethyl)-s-triazme, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trchloromethyl)-s-triazine, 2-n-nonyl-4
  • other examples thereof include the compounds described by F. C. Schaefer et al. in J. Ore. Chem., 29, 1527 (1964 ), for example, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2,4,6-tris(tribromomethll)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2-amino-4-methyl-6-tribromomethyl-s-triazine, 2-metoxy-4-methyl-6-trichloromethyl-s-triazine, and the like, and still further, the compounds described in JP-S62-058241A , for example, the compounds described below and the like.
  • Examples of the (m) azo-based compound which is preferred as the radical initiator, used in the invention include 2,2'-azobisiaobutyronitrile, 2,2'-azobispropionitrile, 1, 1'azobis(cyclohexane- 1-carbonitrile), 2,2'azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), dimethyl-2,2'-azobisisobutyrate, 2,2'azobis(2-methypropionamidoxime), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis ⁇ 2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide ⁇ , 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)pro
  • radical initiator for use in the invention include the above-described (a) aromatic ketones, (b) acylphosphine compounds, (c) aromatic onium salt compounds, (d) organic peroxides, (f) hexaarylbiimidazole compounds, (j) metallocene compounds, and (1) compounds having carbon-halogen bonds, even more preferable examples of the radical initiator include (a) aromatic ketones, (b) acylphosphine compounds, (c) aromatic onium salt compounds, and (1) compounds having carbon-halogen bonds, and particularly preferable examples of the radical initiator include (a) ⁇ -aminoketones represented by the formula (1) of the aromatic ketones and (b) compounds represented by the formula (2) or (3) of the acylphosphine compounds.
  • the content of the radical initiator in the curable composition is preferably 0.1 to 50% by weight, more preferably 0.5 to 30% by weight, and particularly preferably 5 to 20% by weight, based on the total solid content of the curable composition.
  • the radical initiator in the invention is preferably used singly or in combination of two or more kinds thereof
  • a photopolymerization initiator that is preferred from the viewpoint of transparency, when the photopolymerization initiator is made into a 3 g/cm 2 thick film, a compound with an absorbance at a wavelength of 400 nm of no more than 0.3 is preferred; it is more preferably no more than 0.2, and even more preferably no more than 0.1.
  • an ⁇ -aminoketone-based compound and/or an acylphosphine oxide-based compound as the photopolymerization initiator, and it is particularly preferable to use an ⁇ -aminoketone-based compound and an acylphosphine oxide-based compound in combination.
  • the content of the photopolymerization initiator in the curable composition of the invention is preferably in the range of 0.1 to 30% by weight, and more preferably in the range of 0.2 to 20% by weight, on a solid basis.
  • a cationic polymerization initiator for example, compounds that are used for chemically amplified photoresists or cationic photopolymerization are used (for example, " Organic Materials for Imaging", edited by The Japanese Research Association for Organic Electronics Material, Bunshin Publishing Co. (1993), pp. 187-192 ).
  • Examples of the cationic polymerization initiator that is suitable in the invention are as follows.
  • B(C 6 F 5 ) 4 - , PF 6 - , AsF 6 - , SbF 6 - , and CF 3 SO 3 salts of the aromatic onium compounds of diazonium, ammonium, iodimum, sulfonium, phosphonium, and the like can be cited.
  • sulfonated materials that generate a sulfonic acid can be cited.
  • halides that photogenerate a hydrogen halide can also be used.
  • iron arene complexes can be cited.
  • the cationic polymerization initiator one type thereof may be used singly or in combination of two or more kinds thereof.
  • the curable composition of the invention contains an ethylenically unsaturated compound.
  • the ethylenically unsaturated compound which can be used in the invention is not particularly limited as long as it is a compound having an ethylenically unsaturated group, but is preferably a radically polymerizable or cationically polymerizable compound.
  • the radically polymerizable compound in the invention may be any compound as long as it has at least one ethylenically unsaturated bond, and a monomer, an oligomer, a polymer, and the like are included therein.
  • the radically polymerizable compound may be used singly or in combination at any ratio of two or more kinds thereof in order to improve the intended properties. From the viewpoint of controlling the performances such as the reactivity, the physical properties, and the like, it is preferred to use two or more kinds of radically polymerizable compounds in combination.
  • radically polymerizable compound examples include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and the like, and salts thereof, and radically polymerizable compounds including anhydrides having an ethylenically unsaturated bond, acrylonitrile, styrenes, various kinds of unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated urethanes, and the like.
  • unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and the like, and salts thereof
  • radically polymerizable compounds including anhydrides having an ethylenically unsaturated bond, acrylonitrile, styrenes, various kinds of unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated urethan
  • acrylic acid derivatives such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis(4-acryloxypolyethoxyphenyl)propane, neopentylglycol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate,
  • photocurable polymerizable compound materials used in photopolymerizable compositions described in, for example, JP-H07-139983A , JP-H07-31399B , JP-H08-224982A , JP-H10-000863A , JP-H09-134011A , or the like are known, and they may also be applied in the curable composition of the invention.
  • a vinyl ether compound is also preferably used.
  • vinyl ether compounds divinyl ether compounds and trivinyl ether compounds are preferred from the viewpoint of curability, adhesion, and surface hardness, and divinyl ether compounds are particularly preferred.
  • the vinyl ether compound may be used singly or in an appropriate combination of two or more kinds thereof.
  • (meth)acrylic acid esters such as (meth)acrylic-based monomers or prepolymers, epoxy-based monomers or prepolymers, urethane-based monomers or prepolymers, and the like (hereinafter also simply referred to as "acrylate compounds" as appropriate) are preferably used. Even more preferred compounds are as follows.
  • examples thereof include acrylate compounds such as 2-ethylhexyldiglycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxybutyl acrylate, hydroxypivalic acid neopentyl glycol diacrylate, 2-acryloyloxyelhylphthalie acid, methoxy polyethylene glycol acrylate, tetramethylolmethane triacrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, dimethyloltricyclodecane diacrylate, ethoxylated phenyl acrylate, 2-acryloyloxyethylsuccinic acid, nonylphenol ethylene oxide (EO) adduct acrylate, modified glycerin triacrylate, bisphenol A diglycidyl ether acrylic acid adduct, modified bisphenol A diacrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethylhexahydro
  • the monomers listed above have high reactivity, low viscosity, and excellent adhesion to a recording medium.
  • the polymerizable compounds used in the photopolymerizable compositions described in JP-2003-026711A , JP-H04-031467 , JP-H04-041563A , JP-H04-041564A , JP-R05-263012A , JP-H05-263013A , and JP4277936B , or the like can also be used as the ethylenically unsaturated compound in the invention.
  • the compound represented by the formula (I) in order to improve the non-tackiness (suppression of surface Tackiness) and surface smoothness, it is preferred to use the compound represented by the formula (I) in combination with, among the ethylenically unsaturated compounds as described above, a polyfunctional acrylate compound.
  • the content of the polyfunctional ethylenically unsaturated compound is preferably 5 to 80% by weight, and more preferably 40 to 70% by weight, based on the total weight of the curable composition.
  • the content is in the above-mentioned range, the non-tackiness is excellent.
  • a radical ⁇ cationic hybrid coating composition may be employed in which a combination of the radically polymerizable compound and the radical photopolymerization initiator is used together with a combination of the cationically polymerizable compound described below and the cationic polymerization initiator.
  • the radically polymerizable compound is preferred, but a cationically polymerizable compound can also be used.
  • the cationically polymerizable compound that can be used is not particularly limited as long as it is a compound for which a polymerization reaction is initiated by an acid generated from a photo-acid generator and which cures, and various kinds of known cationically polymerizable monomers known as cationically photopolymerizable monomers can be used.
  • a compound having an ethylenically unsaturated bond and the cationically polymerizable compound having no ethylenically unsaturated bond are used in combination.
  • Examples of the cationically polymerizable monomer include epoxy compounds, vinyl ether compounds, oxetane compounds, and the like described in JP-H06-009714A , JP-2001-31892A , JP-2001-40068A , JP-2001-55507A , JP-2001-310938A , JP-2001-310937A , JP-2001-220526A , or the like.
  • a polymerizable compound applied in a photocurable resin of a cationic polymerization system for example, a polymerizable compound applied in a photocurable resin of a cationic polymerization system is known, and in recent years polymerizable compounds applied in photocurable resins of cationic photopolymerization systems sensitized to a visible light wavelength range of 400 nm or more have been disclosed in, for example, JP-H06-043633A and JP-H08-324137A . They can be applied in the curable composition of the invention.
  • the content of the ethylenically unsaturated compound in the curable composition of the invention is preferably in the range of 10 to 97% by weight, more preferably in the range of 30 to 95% by weight, and particularly preferably in the range of 50 to 90% by weight, based on the total weight of the curable composition.
  • the ethylenically unsaturated compound can be used singly or in combination of two or more kinds thereof.
  • the ink composition of the invention contain a colorant.
  • the colorant which can be used in the invention is not particularly limited, and any one can be selected from known colorants such as a pigment, a dye, and the like and used, but the pigment is preferred.
  • organic pigment examples include natural dye-based pigments such as Madder Lake, Logwood Lake, Cochineal Lake, and the like, nitroso-based pigments such as Naphthol Green B, Naphthol Green Y, and the like, nitro-based pigments such as Naphthol Yellow S, Lithol Fast Yellow 2G, and the like, insoluble azo-based pigments such as Permanent Red 4R, Brilliant Fast Scarlet, Hansa Yellow, Benzidine Yellow, and the like, not easily soluble azo-based pigments such as Lithol Red, Lake Red C, Lake Red D, and the like, soluble azo-based pigments such as Brilliant Carmine 6B, Permanent Red F5R, Pigment Scarlet 3B, Bordeaux 10B, and the like, phthalocyanine-based pigments such as Phthalocyanine Blue, Phthalocyanine Green, Sky Blue, and the like, basic dye-based pigments such as Rhodamine Lake, Malachite Green Lake, Methyl Violet Lake, and the like, acidic dye
  • the inorganic pigments include natural inorganic pigments such as clay, barytes, mica, loess, and the like, chromates such as chrome yellow, zinc yellow, barium yellow, and the like, ferrocyanides such as Prussian Blue and the like, sulfides such as Red mercuric sulfide, cadmium yellow, zinc sulfide, antimony white, cadmium red, and the like, sulfates such as barium sulfate, lead sulfate, strontium sulfate, and the like, oxides such as zinc white, titanium white, Bengara, black iron, chromium oxide, and the like, hydroxides such as aluminum hydroxide and the like, silicates such as calcium silicate, ultramarine and the like, carbonates such as calcium carbonate, magnesium carbonate, and the like, carbons such as carbon black, vegetable black, bone black, graphite, and the like, metal powders such as aluminum powders, bronze powders, zinc
  • the colorant which can be used in the invention be added to the ink composition of the invention, and then suitably dispersed in the ink composition.
  • a dispersing device such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloidal mill, an ultrasonic homogenizer, a pearl mill, a wet type jet mill, a paint shaker, and the like can be used.
  • the colorant may be directly mixed with another component in the production of the ink composition of the invention, but in order to improve dispersibility, it may be mixed after being added in advance to a dispersion medium such as a solvent or a radically polymerizable compound used in the invention, and uniformly dispersed or dissolved.
  • a dispersion medium such as a solvent or a radically polymerizable compound used in the invention
  • the colorant in order to prevent the degradation of solvent resistance when there is a residual solvent in a cured image and prevent the VOC (Volatile Organic Compound) problem due to the residual solvent, the colorant is preferably added to a dispersion medium such as a radically polymerizable monomer and then mixed.
  • a dispersion medium such as a radically polymerizable monomer
  • colorants may be used by appropriately selecting one kind or two or more kinds according to the intended purpose of the ink composition.
  • the colorant, the dispersant, and the dispersion medium are selected and for the dispersion conditions and the filtration conditions to be set so that the average particle diameter of colorant particles may be preferably 0.005 to 0.5 ⁇ m, more preferably 0.01 to 0.45 ⁇ m, and even more preferably 0.015 to 0.4 ⁇ m.
  • the average particle diameter of colorant particles may be preferably 0.005 to 0.5 ⁇ m, more preferably 0.01 to 0.45 ⁇ m, and even more preferably 0.015 to 0.4 ⁇ m.
  • the content of the colorant in the ink composition of the invention is appropriately selected according to the color and the use purpose, but is preferably 0.01 to 30% by weight based on the total weight of the ink composition.
  • the curable composition of the invention may include a co-sensitizer.
  • the co-sensitizer has a function of further improving the sensitivity of a sensitizer toward actinic radiation, suppressing the inhibition of polymerization of a polymerizable compound by oxygen, or the like.
  • Examples of such a co-sensitizer include amines, for example, the compounds described in M. R. Sander et al., "Journal of Polymer Society", Vol. 10, p. 3173 (1972 ), JP-S44-020189B , JP-S51-082102A , JP-S52-134692A , JP-S59-138205A , JP-S60-084305A , JP-S62-018537A , JP-S64-033104A , and Research Disclosure No. 33825.
  • amines for example, the compounds described in M. R. Sander et al., "Journal of Polymer Society", Vol. 10, p. 3173 (1972 ), JP-S44-020189B , JP-S51-082102A , JP-S52-134692A , JP-S59-138205A , JP-S60-084305A , JP-S62-018537A
  • co-sensitizer examples include thiols and sulfides, for example, thiol compounds described in JP-S53-000702A , JP-S55-500806T , and JP-S05-142772A , disulfide compounds described in JP-S56-075643A , and the like.
  • amino acid compounds for example, N-phenylglycine and the like
  • organometallic compounds described in JP-S48-042965B for example, tributyltin acetate and the like
  • hydrogen donors described in JP-S55-034414B hydrogen donors described in JP-S55-034414B
  • sulfur compounds described in JP-H06-308727A for example, trithiane and the like
  • phosphorus compounds described in JP-H06-250387A for example, diethylphosphite and the like
  • Si-H and Ge-H compounds described in JP-H08-054735A and the like.
  • the curable composition of the invention may include a surfactant.
  • surfactant examples include those described in JP-S62-173463A and JP-S62-18345 7A , for example, anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, and the like, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, acetylene glycols, polyoxyethylene/polyoxypropylene block copolymers, and the like, and cationic surfactants such as alkylamine salts, quaternary ammonium salts, and the like.
  • anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, and the like
  • nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, acetylene glycols, polyoxy
  • An organofluoro compound or a polysiloxane compound may be used as the surfactant.
  • the organofluoro compound is preferably hydrophobic.
  • examples of the organofluoro compound include fluorine-based surfactants, oil-like fluorine-based compounds (for example, fluorine oil), solid fluorine compound resins (for example, a tetrafluoroethylene resin), and those described in JP-S57-009053B (paragraphs 8 to 17) and JP-S62-135826A .
  • polydimethylsiloxane can be preferably cited as the surfactant.
  • This surfactant can be used singly or in combination of two or more kinds thereof.
  • Other components may be added to the curable composition of the invention as necessary.
  • examples of such other components include a polymerization inhibitor, a solvent, inorganic particles, organic particles, and the like.
  • the polymerization inhibitor may be added from the viewpoint of enhancing the storage stability.
  • the polymerization inhibitor is preferably added at 200 to 20,000 ppm based on the total amount of the curable composition of the invention.
  • polymerization inhibitor examples include hydroquinone, benzoquinone, p-methoxyphenol, TEMPO, TEMPOL, cupferron Al, and the like.
  • the curable compositions of the invention not to contain any solvent so that the curable composition of the invention can react quickly and be cured after coating.
  • a specified solvent may be added.
  • an organic solvent may be used as the solvent, and from the viewpoint of curing speed, it is preferred that substantially no water to be added.
  • the organic solvent may be added in order to improve adhesion to a printing substrate (an image receiving substrate such as paper and the like).
  • a known compound may be added to the curable composition of the invention as necessary.
  • a leveling additive for adjusting film physical properties, a polyester-based resin, a polyurethane-based resin, a vinyl-based resin, an acrylic-based resin, a rubber-based resin, a wax, and the like, which can be appropriately selected and added.
  • Preferred examples of the polyurethane-based resin include a urethane compound having no ethylenically unsaturated bond.
  • Examples of the urethane compound having no ethylenically unsaturated bond include a reaction product of a polyhydric alcohol component with a polyisocyanate component having no aromatic ring structure.
  • polyhydric alcohol component examples include polyhydric alcohols having no aromatic ring structure such as ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, tetramethylene glycol, ditetramethylene glycol, tritetramethylene glycol, 1,4-cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, glycerine, trimethylolethane, trimethylolpropane, pentaerythritol 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate, and
  • polyisocyanate component one having no aromatic ring structure is preferably used.
  • specific examples thereof include one or a mixture of two or more kinds of 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,6-diisocyanate dimercaptoate, 4,4'-methylene bis(cyclohexylisocyanate), methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,3-(isocyanatomethyl)cyclohexane, 1,4-(isocyanatomethyl)cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, and the like.
  • one or a mixture of two or more kinds of 4,4'-methylene bis(cyclohexylisocyanate), methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, and isophorone diisocyanate are preferred from the viewpoint of reduced yellowing or the like.
  • Preferred combinations of specific polyhydric alcohol components and polyisocyanate components are, for example, as follows.
  • urethane compound having no ethylenically unsaturated bond there can be used commercially available products, but when commercially available products containing a solvent are used, it is desirable to use them after removing the solvent.
  • the polyurethane-based resin include a urethane compound having an ethylenically unsaturated bond.
  • Examples of the urethane compound having an ethylenically unsaturated bond include compounds obtained by modifying the above-described urethane compound having no ethylenically unsaturated bond with a hydroxyl group-containing (meth)acrylate.
  • urethane acrylate-based prepolymers known as an active energy curable material
  • a prepolymer in which a component having no aromatic ring structure is used as a polyisocyanate component
  • the general-purpose urethane acrylate prepolymer include a reaction product of a polyether polyol, a polyisocyanate having no aromatic ring structure, and a hydroxyl group-containing (meth)acrylate. This reaction product has an ethylenically unsaturated bond derived from the hydroxyl group-containing (meth)acrylate at an end thereof.
  • urethane acrylate-based prepolymer examples include those described in JP-H05-009247A , JP-H10-030012A , or the like, which include a reaction product of a polyether polyol, a polyisocyanate, and a hydroxy group-containing (meth)acrylate. Also, in the invention, commercially available urethane acrylate-based prepolymers can also be used.
  • polyester-based resin examples include a polyester resin obtained by reacting a polybasic acid with a polyhydric alcohol.
  • a polyester resin obtained by further reacting fat or fatty acids can also be used.
  • the polyester-based resin may or may not have an ethylenically unsaturated bond, but preferably has an ethylenically unsaturated bond.
  • the following polybasic acids and polyhydric alcohols can be preferably used.
  • polybasic acid examples include adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, azelaic acid, sebacic acid, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, himic acid anhydride, maleic anhydride, fumaric acid, itaconic acid, trimellitic anhydride, methylcyclohexenetricarboxylic anhydride, pyromellitic anhydride, and the like.
  • the polybasic acid can be used singly or in combination of two or more kinds thereof.
  • polyhydric alcohol component examples include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, tetramethylene glycol, ditetramethylene glycol, tritetramethylene glycol, 1,4-cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, glycerine, trimethylolethane, trimethylolpropane, pentaerythritol 2,2- dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate, trishydroxymethylaminomethane, pentaeryth
  • polyester resins may be synthesized in the presence of oil, fat, monovalent saturated organic acid, monovalent saturated alcohol, or the like, if desired.
  • oil examples include linseed oil, tung oil, dehydrated castor oil, soybean oil, safflower oil, rice-bran oil, tall oil, castor oil, palm oil, coconut oil and the like.
  • fat examples include fatty acid of linseed oil, fatty acid of tung oil, fatty acid of castor oil, fatty acid of soybean oil, fatty acid of safflower oil, fatty acid of rice-bran oil, fatty acid of tall oil, fatty acid of palm oil, fatty acid of coconut oil, and the like.
  • Examples of the monovalent saturated organic acid include nonanoic acid, octanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, isostearic acid, and the like.
  • Examples of the monovalent saturated alcohol include octyl alcohol, decanol, lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, glycol esters, phenyl glycol, and the like.
  • polyester resins obtained by reacting a polybasic acid such as phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, trimellitic anhydride, and the like with a polyhydric alcohol such as propylene glycol, butylene glycol, hexanediol, neopentyl glycol, octanediol, nonanediol, butyl ethyl propanediol, hydrogenated bisphenol A, hydrogenated bisphenol F, trimethylolpropane, and the like.
  • a polybasic acid such as phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, trimellitic anhydride, and the like
  • a polyhydric alcohol such as propylene glycol, butylene glycol, hexanediol, neopentyl glycol, octan
  • polyester resin having an ethylenically unsaturated bond preferred is a polyester resin obtained by introducing an ethylenically unsaturated bond to the polyester resin having no ethylenically unsaturated bond by reacting the polyester resin with an unsaturated organic acid.
  • polyester resin examples include a polyesteracrylate-based prepolymer obtained by reacting the polyester resin having no ethylenically unsaturated bond with a (meth)acrylic acid.
  • preferred examples thereof include a polyester acrylate-based prepolymer obtained by reacting a (meth)acrylic acid with a polyester produced by reacting a polybasic acid such as phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, trimellitic anhydride, and the like with a polyhydric alcohol such as propylene glycol, butylene glycol, hexanediol, neopentyl glycol, octanediol, nonanediol, butyl ethyl propanediol, hydrogenated bisphenol A, hydrogenated bisphenol F, trimethylolpropane, and the like.
  • the polyester acrylate-based prepolymer commercially available products
  • the polyester resin may have a carboxyl group as well as an acidic group such as a phosphoric acid group, a sulfonic acid group, and the like.
  • Introduction of an acidic group such as a carboxyl group and the like can be carried out, for example, by adjusting the amount of the polybasic acid, the polyhydric alcohol, or the (meth)acrylic acid to be added in the esterification reaction.
  • the acid value of the polyester resin is preferably 5 to 100 mgKOH/g. Within this range, the mechanical strength or water resistance is excellent.
  • a tackifier that does not inhibit polymerization is preferably incorporated.
  • Specific examples of the tackifier include high molecular weight tacky polymers described on p.
  • JP2001-49200A for example, a copolymer formed from an ester of a (meth)acrylic acid and an alcohol having an alkyl group having 1 to 20 carbon atoms, an ester of a (meth)acrylic acid and an alicyclic alcohol having 3 to 14 carbon atoms, or an ester of a (meth)acrylic acid and an aromatic alcohol having 6 to 14 carbon atoms), a low molecular weight tackifying resin having a polymerizable unsaturated bond, and the like.
  • a gel varnish described in JP2000-313850A an amino group-containing high molecular compound described in JP2003-026711A , alkyd resins described in each of JP2005-314511A and JP2005-314832A , or the like can also be used in the curable composition of the invention.
  • the viscosity at 25 to 30°C is preferably 5 to 100 mPa ⁇ s, and more preferably 7 to 75 mPa ⁇ s. Setting the viscosity at 25 to 30° C at the above value enables an image and an overprint having excellent non-tackiness (no surface tackiness) and excellent surface smoothness to be obtained.
  • compositional ratio of the curable composition of the invention is preferably adjusted as appropriate so that the viscosity is in the above range.
  • the surface tension of the curable composition of the invention is preferably 16 to 40 mN/m, and more preferably 18 to 35 mN/m.
  • the method for producing the curable composition of the invention will be described. However, the method is not limited to the following methods.
  • the curable composition of the invention is produced by an ordinary method. That is, an ultraviolet ray curable resin or a prepolymer, a monomer, a polymerization initiator, a polymerization inhibitor, and the like are put into a melting pot and dissolved by heating. Then, a pigment is added thereto and mixed in a mixer, and thereafter or immediately, dispersed using a two-roll mill, a three-roll mill, a jet mill, a ⁇ blade type kneader, a Banbury mixer, a high-speed biaxial continuous mixer, an extruder type kneader, or the like.
  • the pigment may be dispersed in a thermoplastic resin such as a styrene-maleic acid copolymer resin and the like, using a kneader such as a sand mill, a two-roll mill, and the like in advance.
  • a thermoplastic resin such as a styrene-maleic acid copolymer resin and the like
  • a kneader such as a sand mill, a two-roll mill, and the like in advance.
  • a printing method of the invention includes a printing step of printing an ink composition including (component A) a compound represented by the formula (I), (component B) a photopolymerization initiator, (component C) an ethylenically unsaturated compound, and (component D) a colorant on a material to be printed, and a curing step of irradiating ultraviolet rays having a peak wavelength at 375 to 395 nm by a light-emitting diode to cure the printed ink composition.
  • component A a compound represented by the formula (I)
  • component B a photopolymerization initiator
  • component C an ethylenically unsaturated compound
  • component D a colorant on a material to be printed
  • the printing method of the invention includes a printing step of printing an ink composition (an ink composition of the invention) including (component A) a compound represented by the formula (I), (component B) a photopolymerization initiator, (component C) an ethylenically unsaturated compound, and (component D) a colorant on a material to be printed.
  • an ink composition of the invention including (component A) a compound represented by the formula (I), (component B) a photopolymerization initiator, (component C) an ethylenically unsaturated compound, and (component D) a colorant on a material to be printed.
  • preferred examples of the respective components of the ink composition include the respective components of the ink composition of the invention.
  • the material to be printed is not particularly limited, and a known material to be printed may be used.
  • Examples of the material to be printed include printing paper such as coated paper, high-quality paper, medium-quality paper, and the like, plastics, metals, fibers, and the like.
  • the printing step is preferably a printing step of printing the ink composition of the invention on the material to be printed by a printing plate, and more preferably, a printing step of printing the ink composition of the invention on the material to be printed by a printing plate which is attached to a printing machine.
  • the printing method using a printing plate is not particularly limited, and relief printing, lithographic printing, intaglio printing, and stencil printing, such as flexographic printing, offset printing, gravure printing, screen printing, and the like, may be used. Among these, offset printing is particularly preferable.
  • an ink composition is transferred from an original plate to a material to be printed by an offset printing machine.
  • a PS plate a multilayer metal plate, a deep-etch plate, a Wipon plate, a synthetic resin plate, a waterless lithographic plate having a non-image area coated with a silicone compound, or the like is used.
  • the offset printing machine is not particularly limited. For example, a metal plate printing machine, an offset printing proofreading machine, or the like is used.
  • the printing step may be carried out only once for single-color printing or may be carried out twice or more for color printing or the like.
  • the printing method of the invention includes a curing step of irradiating ultraviolet rays having a peak wavelength at 375 to 395 nm by a light-emitting diode to cure the printed ink composition.
  • the ink composition printed on the material to be printed is cured by irradiating ultraviolet rays having a peak wavelength at 375 to 395 nm from a light-emitting diode.
  • a photopolymerization initiator in the ink composition of the invention is excited directly or indirectly by the irradiation of ultraviolet rays to generate an initiation species, such as radical, acid, or base, and the polymerization reaction of a specific monofunctional (meth)acrylate derivative or another polymerizable compound which is used in combination as desired occurs and is promoted because of the function of the initiation species, such that the ink composition is cured.
  • the compound represented by the formula (I) in the system absorbs ultraviolet ray having a peak wavelength at 375 to 395 nm from the light-emitting diode, is put in an excited state, and comes into contact with a polymerization initiator to promote the dissolution of the polymerization initiator.
  • ultraviolet ray having a peak wavelength at 375 to 395 nm from the light-emitting diode
  • a UV-LED ultraviolet ray-emitting diode
  • UV-LED ultraviolet ray-emitting diode
  • ultraviolet rays which are irradiated from the UV-LED to cure the photocurable ink composition or the photocurable coating composition have a peak wavelength at 375 to 395 nm.
  • the peak wavelength of ultraviolet rays which are irradiated onto the photocurable composition or the photocurable coating composition is in a range of 375 to 395 nm, it is possible to select a sensitizer with little absorption in a visible region as a sensitizer favorable to curing, thereby obtaining a cured matter having excellent non-tackiness and excellent hue without having unnecessary absorption in the visible region. That is, if the peak wavelength of ultraviolet rays irradiated by the UV-LED is more than 395 nm, the absorption wavelength of the sensitizer favorable to curing has absorption in the visible region, and the photocurable ink composition and the photocurable coating composition are yellowed. As a result, the hue is deteriorated.
  • a high-power UV-LED which has a peak wavelength of less than 375 nm and is suitable for the object of the invention has a problem in that the cost is high and practicability is low.
  • UV-LED when used as a light source for curing the photocurable ink composition or the photocurable coating composition, various advantages are obtained compared to an ultraviolet ray lamp.
  • the UV-LED has an advantage in that power consumption is low, compared to an ultraviolet ray lamp. For this reason, when a printing apparatus, an overprint apparatus, a device for processing a laminate, or the like using a UV-LED as a light source for curing is configured, it is possible to reduce power consumption.
  • ultraviolet rays which are generated by an ultraviolet ray lamp include ultraviolet rays having a wavelength of 242 nm or less which cause the generation of ozone, ozone is generated in the air. For this reason, when an ultraviolet ray lamp is used, it is necessary to provide discharge means for discharging odor due to the ozone. In contrast, since ultraviolet rays which are generated by the UV-LED do not include ultraviolet rays having such a wavelength, ozone is not generated in the air, and it is not necessary to provide discharge means for discharging the odor due to the ozone.
  • a light source is constituted by a UV-LED, mercury is not required, unlike an ultraviolet ray lamp.
  • a light source using a UV-LED is a light source which is excellent in environmental compatibility compared to a mercury lamp.
  • UV-LED Since light which is generated by the UV-LED does not include infrared rays, and the amount of heat generation is small, it is possible to reduce the influence of heat on a material to be printed or a printing machine.
  • a light source is constituted by a UV-LED, it is possible to reduce the size of an ancillary facility, thereby saving the space for a printing apparatus, an overprint apparatus, a device for processing a laminate, or the like.
  • the UV-LED Since the UV-LED has a long lifespan compared to an ultraviolet ray lamp, it is possible to reduce a burden of maintenance.
  • the UV-LED does not require a waiting time and can be turned on and off instantaneously. Therefore, according to the UV-LED, it is possible to reduce an operation waiting time.
  • UV-LEDs can be used in irradiating ultraviolet rays.
  • the illuminance of ultraviolet rays irradiated from the UV-LED on an irradiation target is preferably 1,000 mV/cm 2 or more, and more preferably 2,000 mV/cm 2 or more.
  • the illuminance is measured with an irradiation distance of 10 mm, and is preferably measured by an Ushio UV Meter 405 (manufactured by Ushio Inc.) with an irradiation distance of 10 mm.
  • the photocurable ink composition and the photocurable coating composition of the invention has sufficient sensitivity even as a low-power UV-LED.
  • the irradiation amount of the UV-LED is preferably in a range of 10 to 4,000 mJ/cm 2 , and more preferably, in a range of 20 to 4,000 mJ/cm 2 .
  • An ultraviolet curing device in which the UV-LED, which is usable in the invention, is used as a light source is not particularly limited.
  • Aicure UD80 Series manufactured by Panasonic Electric Works Co. Ltd. is used.
  • a type having an irradiation width of 750 mm uses a UV-LED, which generates ultraviolet rays having a wavelength of 385 nm ⁇ 10 nm, is used as a light source.
  • Fig. 2 is a schematic configuration diagram of a printing machine which can be used in an embodiment of the printing method of the invention.
  • a printing machine 100 is configured such that five-color printing is carried out, and such that, in addition to an ink composition of four primary colors of cyan (C), magenta (M), yellow (Y), and black (Bk), which is a printing ink of a plurality of different primary colors, for example, specific color printing or complementary color printing is carried out using one specific color (referred to as a specific color) of an ink composition or the like of gold, silver, fluorescent, and pearl.
  • the printing machine 100 includes a sheet feeding section 20, a printing section 30, and a sheet discharging section 40.
  • the sheet feeding section 20 can feed a material to be printed (not shown) to the printing section 30.
  • the printing section 30 can carry out printing on the material to be printed fed from the sheet feeding section 20, and includes a plurality of printing units (in this case, five printing units 30a to 30e in which the primary color images of C, M, Y, and Bk and the specific color image in which specific color printing or complementary color printing is performed are formed).
  • the sheet discharging section 40 can discharge the material to be printed which is printed by the printing section 30 and laminate the material to be printed in the up-down direction.
  • An ultraviolet ray curable ink composition is used as the ink composition, and a drying unit 30f is connected to the end of the printing unit 30e so as to cure the ink composition of the material to be printed which is printed through the printing units 30a to 30e.
  • the material to be printed is fed from the sheet feeding section 20 to the printing section 30, after the fed material to be fed is printed by the printing units 30a to 30e in the printing section 30, the ink composition is cured by the drying unit 30f, and the material to be printed is discharged to the sheet discharging section 40.
  • alignment referred to as registration
  • the material to be printed is fed from the sheet feeding section 20 to the printing section 30 while maintaining the aligned state.
  • Each of the printing units 30a to 30e of the printing section 30 is constituted by a plate cylinder 1, a rubber cylinder 2, and an impression cylinder 3 as a set of main constituent elements.
  • Reference numeral 9a in the printing unit 30a and reference numerals 9b and 9c in the printing units 30b to 30d are all transfer cylinders and are different in size.
  • the transfer cylinder and the impression cylinder have grippers (not shown) which convey the material to be printed with the material to be printed sandwiched therebetween and transfer the material to be printed to the next adjacent cylinder in the conveying direction.
  • a plate for printing is provided in the plate cylinder 1 in each of the printing units 30a to 30e. Ink and water are supplied to the plate, and the ink composition is transferred to the rubber cylinder 2 along the plate. The ink composition transferred to the rubber cylinder 2 is further transferred to the material to be printed which is conveyed while being sandwiched between the rubber cylinder 2 and the impression cylinder 3 facing the rubber cylinder 2. Therefore, printing can be sequentially carried out on the material to be printed which is fed from the sheet feeding section 20, by the plate provided in each of the five plate cylinders 1.
  • an ultraviolet irradiation portion T is provided which irradiates ultraviolet rays onto the ink composition of the material to be printed, which is printed and conveyed, to cure the ink composition.
  • Fig. 3(a) is a perspective view showing the arrangement relationship between the impression cylinder and a light-emitting diode in the ultraviolet irradiation portion T.
  • Fig. 3(b) is a front view of a substrate having light-emitting diodes in the ultraviolet irradiation portion T.
  • the ultraviolet irradiation portion T includes 44 light-emitting diodes 4 which have an irradiation axis in a direction substantially perpendicular to the surface of the impression cylinder 3, and the light-emitting diodes 4 are arranged above the impression cylinder 3.
  • the gap between the light-emitting diodes 4 and the impression cylinder 3 is preferably as small as possible from the viewpoint of curing efficiency, the gap is preferably set such that the light-emitting diodes 4 do not come into contact with the material to be printed.
  • the 44 light-emitting diodes 4 are arranged on a straight line at predetermined intervals (regular intervals) in the width direction of the material to be printed (impression cylinder 3) to irradiate ultraviolet rays over the entire width direction of the impression cylinder 3.
  • 11 light-emitting diodes 4 are provided in a single oblong substrate 5.
  • Four substrates 5 are connected to each other in the width direction of the material to be printed (impression cylinder 3), and support members 6 (a part of one end is shown in Fig. 3(b)) are respectively attached to the ends of the substrates 5 on both sides, such that the four substrates 5 are supported by the left and right support members 6 and 6 at a predetermined distance (predetermined height) from the impression cylinder 3.
  • a method of preparing an overprint of the invention includes a coating step of coating a coating composition including (component A) a compound represented by the formula (I), (component B) a photopolymerization initiator, and (component C) an ethylenically unsaturated compound on a printed matter, and a curing step of irradiating ultraviolet rays having a peak wavelength at 375 to 395 nm by a light-emitting diode to cure the coating composition thus coated.
  • a coating step of coating a coating composition including (component A) a compound represented by the formula (I), (component B) a photopolymerization initiator, and (component C) an ethylenically unsaturated compound on a printed matter, and a curing step of irradiating ultraviolet rays having a peak wavelength at 375 to 395 nm by a light-emitting diode to cure the coating composition thus coated.
  • An overprint of the invention has an overprint layer which is formed by irradiating ultraviolet rays having a peak wavelength at 375 to 395 nm by a light-emitting diode to cure the coating composition of the invention on a printed matter.
  • the overprint has at least one overprint layer on the surface of a printed matter obtained by a printing method, such as electrophotographic printing, ink jet printing, screen printing, flexographic printing, lithographic printing, intaglio printing, or relief printing.
  • a printing method such as electrophotographic printing, ink jet printing, screen printing, flexographic printing, lithographic printing, intaglio printing, or relief printing.
  • the printing method is not particularly limited, and known methods may be used.
  • the overprint layer may be formed in a part of the printed matter or may be formed over the entire surface of the printed matter. In the case of a duplex printed matter, the overprint layer is preferably formed over both surfaces of a printing base material. Needless to say, the overprint layer may be formed in an unprinted portion in a printed matter.
  • the thickness of the overprint layer is preferably in a range of 1 to 10 ⁇ m and more preferably, in a range of 3 to 6 ⁇ m.
  • a method of measuring the thickness of the overprint layer is not particularly limited, a method may be used in which the cross-section of the overprint is observed and measured by an optical microscope or the like.
  • the coating step may be a step of coating a coating composition on the surface of a three-dimensional structure.
  • the three-dimensional structure is not particularly limited, and the coating composition of the invention can be coated on a known object as desired.
  • the ink composition of the invention may be coated as desired instead of the coating composition of the invention.
  • the method of preparing an overprint includes a coating step of coating a coating composition including (component A) a compound represented by the formula (I), (component B) a photopolymerization initiator, and (component C) an ethylenically unsaturated compound on a printed matter.
  • a liquid film coating device which is commonly used can be used.
  • the liquid film coating device include a roll coater, a rod coater, a blade, a wire-wound bar, a dip coater, an air knife, a curtain coater, a slide coater, a doctor knife, a screen coater, a gravure coater, for example, an offset gravure coater, a slot coater, an extrusion coater, and the like.
  • These devices may be used in the same manner as normal, and examples thereof include direct and reverse roll coating, blanket coating, dampner coating, curtail coating, lithographic coating, screen coating, gravure coating, and the like.
  • coating and curing of the coating composition, of the invention are carried out using two or three roll coaters and UV curing stations.
  • heating may be carried out
  • the coating amount of the coating composition of the invention is preferably in a range of 1 to 10 g/m 2 , and more preferably, in a range of 3 to 6 g/m 2 as a weight per unit area.
  • the amount per unit area of the overprint layer formed in the overprint obtained by the method of preparing an overprint of the invention is preferably in a range of 1 to 1 g/m 2 , and more preferably, in a range of 3 to 6 g/m 2 .
  • the printing base material is not particularly limited, and known materials may be used.
  • image receiving paper is preferably used, plain paper or coated paper is more preferably used, and coated paper is still more preferably used.
  • coated paper double-sided coated paper is preferable because a full color image can be duplex-printed richly.
  • the paper weight is preferably in a range of 20 to 200 g/m 2 , and more preferably, in a range of 40 to 160 g/m 2 .
  • the method of preparing an overprint of the invention includes a curing step of irradiating ultraviolet rays having a peak wavelength at 375 to 395 nm by a light-emitting diode to cure the coating composition thus coated.
  • a form of the curing step in the printing method of the invention can be preferably used.
  • a method for processing a laminate of the invention includes a coating step of coating a coating composition including (component A) a compound represented by the formula (1), (component B) a photopolymerization initiator, and (component C) an ethylenically unsaturated compound on a printed matter, a laminating step of laminating a laminate film on the printed matter having the coating composition coated thereon, and a curing step of irradiating ultraviolet rays having a peak wavelength at 375 to 395 no by a light-emitting diode to cure the coating composition thus coated.
  • the irradiation of ultraviolet rays having a peak wavelength, at 375 to 395 nm by the light-emitting diode in the coating step and the curing step in the method for processing a laminate of the invention are the same as the coating step and the irradiation of ultraviolet rays having a peak wavelength at 375 to 395 nm by the light-emitting diode in the curing step of the method of preparing an overprint of the invention, and the preferred ranges are also the same.
  • the method for processing a laminate of the invention includes a laminating step of laminating a laminate film on the printed matter having the coating composition coated thereon.
  • the coating composition preferably serves as an adhesive of the printed matter and the laminate film.
  • the laminate film which can be used in the laminating step is not particularly limited, and a known laminate film such as a resin film and the like can be used.
  • the laminate film may be a film having an uneven pattern even in a smooth film as desired.
  • the method for processing a laminate of the invention includes a curing step of irradiating ultraviolet rays having a peak wavelength at 375 to 395 nm by a light-emitting diode to cure the coating composition thus coated.
  • the irradiation of ultraviolet rays may be carried out from the side to which the laminate film is attached, or if the base material of the printed matter is a transparent base material, the irradiation of ultraviolet rays may be carried out from the opposing side or both sides. It is preferable that irradiation is carried out from the side to which the laminate film is attached.
  • the laminate film is a plate which has concaves and convexes formed in the surface thereof overlapping the coating composition.
  • the concaves and convexes of the plate are transferred to a coated film, such that the glossiness (matt, gloss) of a coated surface is adjusted.
  • An arbitrary uneven pattern or a hologram may be formed.
  • the method for processing a laminate of the invention preferably includes a separating step of separating the laminate film from the laminated printed matter.
  • the separating step may be before or after the curing step, when the laminate film and the coating composition come into contact with each other and cured with adhesiveness, the separating step may be carried out before the curing step.
  • a device for processing a laminate which can be used in the method for processing a laminate of the invention is not particularly limited.
  • the devices described in JP-H11-350398A , JP-H06-008400A , JP-S56-037398A , JP-S63-278847A , and JP-H08-325991A are used.
  • Fig. 4 is a diagram showing the schematic configuration of a coating device 200 which can be used in the method for processing a laminate of the invention.
  • a paper material 202 is held around a paper material unwinding device 204 as a roll 203, and the unwound paper material 202 is guided by a guide roller 205 and wound around a paper material winding device 206 as a roll.
  • the paper material unwinding device 204, the guide roller 205, and the paper material winding device 206 constitute a paper material conveying device as a whole, and a coating device which coats a coating composition, a curing device, and a separating device are sequentially provided in the course of conveying the paper material 202 by the guide roller 205.
  • an elongated laminate film 210 which has a specific light transmission characteristic, that is, transmits ultraviolet rays having a peak wavelength at 375 to 395 nm generated by the light-emitting diode in this embodiment is held around a laminate film unwinding device 212 as a roll 211.
  • the unwound laminate film 210 is guided by a guide roller 213 and wound around a laminate film winding device 214 as a roll.
  • the laminate film unwinding device 212, the guide roller 213, and the laminate film winding device 214 constitute a laminate film conveying device as a whole, and a curing device and a separating device are sequentially provided in the course of conveying the laminate film 210 by the guide roller 213.
  • the above-described coating device includes a storage tank 215 which stores the coating composition, a roller 217 which coats the coating composition in the storage tank 215 uniformly on the surface of a coating roller 216, and the coating roller 216 which is driven to rotate in the conveying direction of the paper material 202, and is provided near the upstream side of the curing device.
  • the above-described curing device includes a specific light transmissive pressing roller 220 which is in contact with the laminate film 210 and driven to rotate in the conveying direction of the laminate film 210, a receiving-side pressing roller 221 which is rotatably provided to press the conveyed laminate film 210 and paper material 202 in an overlapping manner along with the pressing roller 220, a first light-emitting diode 222 which is embedded in the pressing roller 220, and a second light-emitting diode 223 which is provided near the pressing rollers 220 and 221 on the downstream side in the conveying direction.
  • the above-described separating device includes a separating roller 224 which guides the laminate film 210 in a direction distant from the cured coated film formed on the paper material 202, and a pair of holding rollers 225 which guides the paper material 202 to face the separated laminate film 210 while sandwiching the paper material 202 therebetween.
  • the laminate film 210 is preferably a material which has a smooth surface so as to prevent the penetration or adhesion of the coating composition.
  • a film made of an ultraviolet transmissive material such as polypropylene, polyethylene, or a polyethylene composite, is used.
  • the laminate film 210 is preferably an unprocessed film which is not subject to treatment such as corona treatment and the like.
  • the laminate film 210 is not limited to one having a smooth surface, and can be appropriately selected depending on how the surface of the resin film is processed. For example, when the resin film is formed to have a polished surface having glossiness, the laminate film 210 having a smooth surface is selected and used. When the resin film is desired to be removed by polishing, the laminate film 210 having a matted surface is selected. When a pattern or figure having fine concaves and convexes is desired to be formed in the resin film, a laminate film with a pattern or a figure having small concaves and convexes, for example, embosses in the surface is used as a plate. When a hologram having ultrafine concaves and convexes is formed in the resin film, a laminate film having ultrafine concaves and convexes opposite to the hologram to be formed in the surface thereof is used as an inverting transfer plate.
  • an inverting transfer plate (laminate film) with concaves and convexes in the surface thereof
  • a separating agent is coated on the original plate with concaves and convexes by means of printing or the like, and a thermal-melt resin, for example, molten polyethylene is then coated.
  • the molten resin is separated after curing, and the separated cured coated film is used as an inverting transfer plate (laminate film 210) with the concaves and convexes of the original plate transferred.
  • a plate for printing can be generally inexpensive and easy. Therefore, even using inverting transfer, a plate for coating can be created easily and inexpensively, and a plate, such as a hologram, having ultrafine concaves and convexes can be created easily and inexpensively while maintaining sufficient precision.
  • the original plate When an original plate is created by printing, the original plate can be created by known printing, such as gravure printing, flexographic printing, offset printing, or screen printing, and ink printed portions are made convex.
  • a figure or the like may be directly printed on the surface of a laminate film to form concaves and convexes of ink, and the concaves and convexes may be transferred to a resin coated film.
  • a separating agent is preferably coated on the printed surface of the laminated film.
  • the pressing roller 220 is constituted by, for example, a transparent glass tube, and the material thereof is not particularly limited insofar as the material has strength resistant to pressing and a required ultraviolet transmission characteristic.
  • the method for processing a laminate of the invention will be specifically described in connection with the action of the coating device 200 configured as above.
  • the paper material 202 is conveyed from the paper material unwinding device 204 to the paper material winding device 206 by the paper material conveying device while being guided by the guide roller 205.
  • the coating roller 216 which is provided near the upstream side of the curing device is driven to reversely rotate, and the coating composition in the storage tank 215 is stuck to the outer circumferential surface of the coating roller 216 through the roller 217 and coated on one surface of the paper material 202 being conveyed.
  • the paper material 202 with the coated film of the coating composition formed in the above-described manner is wound between a pair of pressing rollers 220 and 221 being driven to rotate in a state where the surface on the side with no coated film comes into contact with the pressing roller 221.
  • the laminate film 210 is guided by the guide roller 213 and conveyed from the laminate film unwinding device 212 to the laminate film winding device 214 by the laminate film conveying device.
  • the laminate film 210 is wound between the pressing rollers 220 and 221 along with the paper material 202, and overlaps the paper material 202 through the coated film.
  • Ultraviolet rays from the first light-emitting diode 222 are irradiated onto the coated film pressed and bonded to the surface of the paper material 202 through the pressing roller 220 and the laminate film 210.
  • the paper material 202 and the laminate film 210 are sandwiched and pressed between the pressing rollers 220 and 221, such that the coated film is pressed and bonded to the laminate film 210, and cured to some extent.
  • a method is also considered in which a coating composition is coated on a film side to form a coated film, the film and a paper material are pressed and bonded to each other by the pressing rollers, ultraviolet rays are irradiated to cure the coated film, and external force is applied after curing to separate the laminate film from the paper material and to transfer the coated film to the surface of the paper material.
  • the laminate film 210 and the paper material 202 which overlap each other by the above-described half-cured coated film are conveyed from the pressing rollers 220 and 221 to the second light-emitting diode 223.
  • Ultraviolet rays are irradiated onto the coated film again through the laminate film 210, such that the coated film is completely cured.
  • the coated film formed on the paper material 202 is thin, and there is no oxygen alienation in a chemical reaction because the coated film is exposed to external air in the course of being conveyed. For this reason, the curing of the coated film is finished rapidly, and cure reversion does not occur.
  • the coated film is completely cured, the paper material 202 and the laminate film 210 are conveyed to the separating device, the laminate film 210 is guided and separated by the separating roller 224 in a direction distant from the paper material 202, and the paper material 202 against the separated laminate film 210 is sandwiched by a pair of holding rollers 225.
  • the paper material 202 whose surface is coated with the cured coated film in the above-described manner is wound around the paper material winding device 206 as a roll. Meanwhile, the laminated film 210 is wound around the laminate film winding device 214 as a roll.
  • the laminate film 210 is in contact with the coated film only during a period from the pressure bonding/curing step by the pressing rollers 220 and 221, or the like to the separating step, such that it is possible to reduce the time for which the laminate film 210 is in contact with the coating composition. Simultaneously, since the laminate film 210 is in contact with the coated film in a half-cured state, it is possible to suppress deterioration (deterioration in smoothness due to pressure bonding and separating) of the surface of the laminate film 210 in contact with the coated film. Therefore, the laminate film 210 can be repeatedly used in a state where a function of smoothing the coated film is maintained.
  • Fig. 5 is a diagram showing a coating device 201 according to an embodiment different from that described above.
  • the surface of a sheet 230 is coated with a film of an ultraviolet ray curable resin.
  • the same portions as those in the above-described embodiment are represented by the same reference numerals, and overlapping description will not be repeated.
  • a paper material conveying device includes a feed device 231 which feeds the sheets 230 one by one, and a stock device 232 which sequentially accommodates the coated sheets 230 in an overlapping manner. Since the sheets 230 are not continuously elongated, the feed device 231 continuously and sequentially feeds the sheets 230 to a resin coating device and between the pressing rollers 220 and 221, such that the coated film formed on the sheets 230 can be coated smoothly with a strong bonding force.
  • the laminate film 210 is endless, and a film driving roller 233 is provided to drive and convey the endless laminate film 210. That is, if the driving roller 233 is driven to rotate by a driving unit (not shown), the endless laminate film 210 is sequentially and circularly conveyed to the curing device, the separating device, and the curing device.
  • the laminate film 210 overlaps the coated film of the coating composition formed on the sheet 230 by the pressing rollers 220 and 221, and the coated film and the surface of the laminate film 210 are pressed and bonded to each other. Simultaneously, ultraviolet rays are irradiated from the first liglit-emitting diode 222 to half-cure the coated film, the coated film is completely cured by ultraviolet irradiation from the second light-emitting diode 223, and subsequently only the laminate film 210 is separated from the sheet 230 by the separating roller 224.
  • the same resin film as in the foregoing embodiment can be formed on the surface of the sheet 230 to coat the sheet 230.
  • any coating device may be used insofar as the coating device can coat the coating composition on the surface of the paper material 202.
  • a form in which the coating composition is coated by blowing through a spray, gravure, flexography, or a bar coater may be used.
  • the second light-emitting diode 223 may not be provided depending on the components in the coating composition or the irradiation amount of the first light-emitting diode 222, and the coated film may be completely cured only by the first light-emitting diode 222.
  • the first light-emitting diode 222 may not be provided and only the second light-emitting diode 223 may be provided.
  • the printing method of the invention, the method of preparing an overprint of the invention, and the method for processing a laminate of the invention may include known steps other than the above-described steps.
  • Ebecryl 605 bisphenol A epoxy diacrylate, manufactured by Cytec Surface Specialties
  • An electrophotographically printed matter obtained using double-sided coated paper output from a digital printer (DC8000) manufactured by Fuji Xerox Co., Ltd. was coated on one side with a coating composition at a film thickness of 5 g/m 2 using a bar coater.
  • the coating film thus obtained was exposed with an illumination intensity of 4,0 W/cm 2 for 0.3 seconds using an Aicure UD80 (manufactured by Panasonic Electric Works Co., Ltd.) set up at an interval of 10 mm from the electrophotographically printed matter, thus preparing an overprint sample.
  • the non-tackiness after exposure was evaluated by feeling. The evaluation criteria are shown below.
  • An overprint sample was prepared by coating a polyethylene terephthalate (PET) film at a thickness of 5 g/m 2 using a bar coater, and exposing the coating film thus obtained with an illumination intensity of 4.0 W/cm 2 for 0.3 seconds using an Aicure UD80 (manufactured by Panasonic Electric Works Co., Ltd.) set up at an interval of 10 mm from the material to be printed.
  • the PET film thus obtained was visually evaluated, sensory evaluation was carried out for hue (transparency), chromaticity indices a and b were measured using a colorimeter CR-100 manufactured by Monica Minolta Sensing, Inc., and a combined evaluation was made in accordance with the criteria below. The results are given in Table 1.
  • Example 1 As a result of evaluation by the methods above, the coating composition of Example 1 gave "A” for non-tackiness and "O" for transparency.
  • a coating composition was produced by the same method as in Example 1 except that 8% by weight of the polymerization initiator 1 (18% by weight each in total) was used instead of the compound represented by the formula (I). Further, evaluation of performance was carried out in the same manner as in Example 1.
  • each of the coating compositions was prepared by the same method as in Example 1 except that the compound represented by the formula (I) and the polymerization initiator were changed to the compounds described in Table 1 or 2. Moreover, when two kinds of the photopolymerization initiators were used, they were each used in an amount of 5% by weight. Further, evaluation of performance was also carried out in the same manner as in Example 1.
  • a coating composition was prepared by the same method as in Example 1 except that 8% by weight of dodecyl acrylate was used instead of the compound (I-1) represented by the formula (I). Further, evaluation of performance was also carried out in the same manner as in Example 1.
  • a solvent of Polyurethane 520 (polyurethane including an aliphatic polyisocyanate component and a polyhydric alcohol component having no aromatic cyclic structure, manufactured by Arakawa Chemical Industries, Ltd.) was distilled off at 100°C under reduced pressure of 15 to 40 kPa, to obtain a urethane compound (Ala.)
  • a urethane compound (Ala) was distilled off at 100°C under reduced pressure of 15 to 40 kPa, to obtain a urethane compound (Ala.)
  • 40 parts of trimethylolpropanepropoxy triacrylate (Aronix M-310 manufactured by Toagosei Co., Ltd.) having a surface tension of 39 mN/m at 20°C to produce a liquid component (Ala).
  • a white ink composition having a tack value of 15 was produced by mixing the following components in the formulation mentioned below, and then milling and stirring the mixture by using a three-roll mill.
  • TIPAQUE CR-58 manufactured by Ishihara Sangyo Kaisha Ltd. was used as a titanium oxide.
  • the "tack" in the tack value above refers to a restoring force of the ink composition layer in a predetermined width between the two rotating rollers which is generated by shearing of the ink layer on the surfaces of the rollers.
  • the tack value is a value measured with a rotary tack meter designed for measuring the tack (see JIS K5700).
  • This white ink composition was printed in a film thickness of 1.5 ⁇ m by offset printing method on a steel panel (200 ⁇ m thick) pre-coated with a polyester to prepare an uncured panel. Then, the following tests were carried out by using this uncured panel. The results are shown in Table 3.
  • the uncured panel was exposed with an illumination intensity of 4.0 W/cm 2 for 1 second using an Aicure UD80 (manufactured by Panasonic Electric Works Co.. Ltd.) set up at an interval of 10 mm, and the non-tackiness after exposure was evaluated by feeling.
  • the evaluation criteria are shown below.
  • the uncured panel was exposed with an illumination intensity of 4.0 W/cm 2 for 0.5 seconds using an Aicure UD80 (manufactured by Panasonic Electric Works Co., Ltd.) set up at an interval of 10 mm, and the panel obtained was evaluated visually for a sensory test of the hue.
  • the evaluation criteria are shown below.
  • An uncured panel was prepared by the same method as in Example 67 except that 3 parts of the polymerization initiator 1 (6 parts in total) was used instead of the compound (I-1) represented by the formula (1). Further, evaluation of performance was carried out in the same manner as in Example 67.
  • Uncured panels were prepared by the same method as in Example 67 except that the compound represented by the formula (I) and the photopolymerization initiator were changed to the compounds in Table 3 or 4. Further, when two kinds of the photopolymerization initiators were used, they were each used in an amount of 1.5 parts. Further, evaluation of performance was also carried out in the same manner as in Example 67.
  • the white, yellow, red, blue, green, and black ink composition in this order were printed on plain paper (manufactured by Fuji Xerox Co., Ltd., full-color plain paper JV649) at a film thickness of 1.5 ⁇ m for each of the colors, by an offset printing method.
  • the ink composition was cured by exposing it for each of the colors at an illumination intensity of 4.0 W/cm 2 for 0.5 seconds using an Aicure UD80 (manufactured by Panasonic Electric Works Co., Ltd.) above.
  • the non-tackiness after exposure was evaluated by feeling, and as a result, the non-tackiness was A and the hue was O.
  • the 6-color printed pattern was a clear printed matter, from which an oblong photographic image including images of people could be obtained.
  • the non-tackiness after 6-color printing and exposure was evaluated by touch feeling, and as a result, the non-tackiness was A, and thus, a printed matter having a good hue could be obtained.
  • PLATE CYLINDER 1: PLATE CYLINDER, 2: RUBBER CYLINDER, 3: IMPRESSION CYLINDER, 4: LIGHT-EMITTING DIODE, 5: SUBSTRATE, 6: SUPPORT MEMBER, 9a, 9b, 9c: TRANSFER CYLINDERS, 20: SHEET FEEDING SECTION.
  • PRINTING SECTION 30: PRINTING SECTION, 30a to 30e: PRINTING UNITS, 30f: DRYING UNIT, 40: SHEET DISCHARGING SECTION, 100: PRINTING MACHINE, S: CONTROLLER, T: ULTRAVIOLET IRRADIATION PORTION, 200, 201: COATING DEVICE, 202: PAPER MATERIAL, 203: ROLL, 204: PAPER MATERIAL UNWINDING DEVICE, 205: GUIDE ROLLER, 206: PAPER MATERIAL WINDING DEVICE, 210: LAMINATE FILM, 211: ROLL, 212: LAMINATE FILM UNWINDING DEVICE, 213: GUIDE ROLLER, 214: LAMINATE FILM WINDING DEVICE, 215: STORAGE TANK, 216: COATING ROLLER, 217: ROLLER, 220.

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* Cited by examiner, † Cited by third party
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* Cited by examiner, † Cited by third party
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Citations (106)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4420189B1 (de) 1965-06-03 1969-08-30
JPS4537377B1 (de) 1965-06-03 1970-11-27
US3567453A (en) 1967-12-26 1971-03-02 Eastman Kodak Co Light sensitive compositions for photoresists and lithography
JPS4642363B1 (de) 1968-10-09 1971-12-15
JPS473981B1 (de) 1968-06-11 1972-02-03
JPS476416B1 (de) 1968-04-16 1972-02-23
JPS4842965B1 (de) 1968-04-02 1973-12-15
GB1388492A (en) 1971-09-03 1975-03-26 Minnesota Mining & Mfg Chromophore-substituted halomethyl-s-triazines
JPS5182102A (en) 1974-12-10 1976-07-19 Basf Ag Insatsuinki oyobi hifukuzairyonotameno hikarijugokanonaketsugozai
JPS52134692A (en) 1976-05-04 1977-11-11 Fuji Photo Film Co Ltd Photopolymerizable composition
JPS53702A (en) 1975-12-23 1978-01-06 Dynachem Corp Adhesion promoting agent for polymerized film
JPS53133428A (en) 1977-04-25 1978-11-21 Hoechst Ag Radiation sensitive copying constitute
JPS5534414B2 (de) 1972-06-02 1980-09-06
JPS55500806A (de) 1978-10-19 1980-10-16
JPS5637398A (en) 1979-09-03 1981-04-11 Takashi Murase Method and apparatus for polishing paper surface
JPS5675643A (en) 1979-11-07 1981-06-22 Hoechst Ag Photopolymerizable mixture and photopolymerizable copying material using same
JPS579053B2 (de) 1978-01-09 1982-02-19
JPS5730704A (en) 1980-06-24 1982-02-19 Bayer Ag Photopolymerizable mixture containing aroylphosphoric acid ester as photoinitiator
US4318791A (en) 1977-12-22 1982-03-09 Ciba-Geigy Corporation Use of aromatic-aliphatic ketones as photo sensitizers
US4343891A (en) 1980-05-23 1982-08-10 Minnesota Mining And Manufacturing Company Fixing of tetra (hydrocarbyl) borate salt imaging systems
EP0109773A2 (de) 1982-10-25 1984-05-30 Minnesota Mining And Manufacturing Company Dispersionsaufzeichnungsmaterialien mit Tetra(hydrocarbyl)-Boratsalzen
EP0109772A2 (de) 1982-10-25 1984-05-30 Minnesota Mining And Manufacturing Company Fixierung von Aufzeichnungsmaterialien mit Tetra(hydrocarbyl)-Boratsalzen
JPS59138205A (ja) 1983-01-20 1984-08-08 チバ−ガイギ−　アクチエンゲゼルシヤフト 被覆組成物およびその硬化方法
JPS59152396A (ja) 1983-02-11 1984-08-31 チバ−ガイギ−　アクチエンゲゼルシヤフト メタロセン，その製造方法およびメタロセンを含む光重合性組成物
JPS59174831A (ja) 1983-03-24 1984-10-03 Fuji Photo Film Co Ltd 光重合性組成物
DE3337024A1 (de) 1983-10-12 1985-04-25 Hoechst Ag, 6230 Frankfurt Lichtempfindliche, trichlormethylgruppen aufweisende verbindungen, verfahren zu ihrer herstellung und diese verbindungen enthaltendes lichtempfindliches gemisch
JPS6084305A (ja) 1983-08-30 1985-05-13 バスフ　アクチェン　ゲゼルシャフト 光重合可能な混合物
JPS6026403B2 (ja) 1977-05-17 1985-06-24 メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング 不飽和化合物の光重合用光増感剤
JPS61151197A (ja) 1984-12-20 1986-07-09 チバ‐ガイギー　アーゲー チタノセン類およびこれらのチタノセン類を含有する照射重合開始剤
JPS61194062A (ja) 1985-02-21 1986-08-28 メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング チオ置換ケトン化合物を用いる光重合開始剤
JPS6218537A (ja) 1985-07-16 1987-01-27 ザ・ミ−ド・コ−ポレ−シヨン 共開始剤として第三アミンを含有する感光性マイクロカプセルを用いた造像材料
JPS626223B2 (de) 1979-03-06 1987-02-09 Fuji Photo Film Co Ltd
JPS6258241A (ja) 1985-09-09 1987-03-13 Fuji Photo Film Co Ltd 感光性組成物
JPS6281345A (ja) 1985-09-28 1987-04-14 チバ―ガイギー　アクチェンゲゼルシャフト 共重合性光開始剤
JPS62135826A (ja) 1985-12-09 1987-06-18 Konishiroku Photo Ind Co Ltd 熱現像感光材料
JPS62173463A (ja) 1986-01-28 1987-07-30 Fuji Photo Film Co Ltd 画像形成方法
JPS62183457A (ja) 1986-02-07 1987-08-11 Fuji Photo Film Co Ltd 画像形成方法
JPS6341484A (ja) 1986-08-01 1988-02-22 チバ−ガイギ−　ア−ゲ− チタノセン、それらの製造法およびそれらを含有する組成物
JPS6314340B2 (de) 1980-09-17 1988-03-30 Fuji Photo Film Co Ltd
JPS63138345A (ja) 1986-11-21 1988-06-10 イーストマン　コダック　カンパニー 写真像形成性システム
JPS63142345A (ja) 1986-11-21 1988-06-14 イーストマン　コダック　カンパニー アジニウム活性化剤を含む画像高形成性組成物
JPS63142346A (ja) 1986-11-21 1988-06-14 イーストマン　コダック　カンパニー ネガ形フォトレジスト
JPS63143537A (ja) 1986-11-21 1988-06-15 イーストマン　コダック　カンパニー ネガ型フォトレジスト
JPS6340799B2 (de) 1978-07-14 1988-08-12 Basf Ag
EP0284561A2 (de) 1987-03-26 1988-09-28 Ciba-Geigy Ag Neue alpha-Aminoacetophenone als Photoinitiatoren
JPS63278847A (ja) 1987-05-12 1988-11-16 Hamamatsu Seisakusho:Kk 枚葉印刷紙面の艶出し装置
JPS6429997A (en) 1987-07-25 1989-01-31 Nittan Co Ltd Environmental abnormality alarming facility
JPS6433104A (en) 1987-06-25 1989-02-03 Ciba Geigy Ag Photopolymerizable composition
JPS6434242A (en) 1987-07-30 1989-02-03 Idemitsu Kosan Co Material for preserving freshness of food
JPH0195788A (ja) 1987-10-08 1989-04-13 Chisso Corp ラットＮＡＤＨ−チトクロムｂ↓５環元酵素ゲノムＤＮＡ
JPH01152109A (ja) 1987-12-09 1989-06-14 Toray Ind Inc 光重合性組成物
JPH01304453A (ja) 1988-06-02 1989-12-08 Toyobo Co Ltd 光重合性組成物
JPH02249A (ja) 1987-12-01 1990-01-05 Ciba Geigy Ag チタノセンおよびそれを含有する光重合性組成物
JPH024705A (ja) 1988-03-24 1990-01-09 Dentsply Internatl Inc 光硬化性組成物用チタナート開始剤
JPH02211452A (ja) 1988-12-01 1990-08-22 Polychrome Corp 光開始剤
JPH0431467A (ja) 1990-05-25 1992-02-03 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化性オーバーコートワニス
JPH0441563A (ja) 1990-06-08 1992-02-12 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化性オーバーコートワニス
JPH0441564A (ja) 1990-06-08 1992-02-12 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化性オーバーコートワニス
JPH059247A (ja) 1991-07-02 1993-01-19 Dainippon Ink & Chem Inc 活性エネルギー線硬化型樹脂組成物
JPH0529234A (ja) 1991-07-25 1993-02-05 Fujitsu Ltd エピタキシヤル成長法
JPH05142772A (ja) 1991-11-26 1993-06-11 Fuji Photo Film Co Ltd 光重合性組成物
JPH05263013A (ja) 1992-03-19 1993-10-12 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化性オーバーコートワニス
JPH05263012A (ja) 1992-03-19 1993-10-12 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化性オーバーコートワニス
JPH05281728A (ja) 1992-04-01 1993-10-29 Fuji Photo Film Co Ltd 光重合性組成物
JPH069714A (ja) 1992-06-29 1994-01-18 Sumitomo Chem Co Ltd 光重合性組成物及び光制御板の製造方法
JPH068400A (ja) 1992-06-26 1994-01-18 Hamamatsu Seisakusho:Kk 紙面加工方法及びその装置
JPH0643633A (ja) 1992-05-06 1994-02-18 Kyowa Hakko Kogyo Co Ltd 化学増幅型レジスト組成物
JPH0626483B2 (ja) 1987-09-14 1994-04-13 セイレイ工業株式会社 超音波センサーを用いた耕深制御装置
JPH06250387A (ja) 1993-03-01 1994-09-09 Sumitomo Chem Co Ltd キノンジアジドスルホン酸エステルの製法及び該製法により得られたキノンジアジドスルホン酸エステルを含有してなる感放射線性樹脂組成物
JPH06308727A (ja) 1993-04-19 1994-11-04 Fuji Photo Film Co Ltd 光重合性組成物
JPH0731399B2 (ja) 1984-12-21 1995-04-10 三菱化学株式会社 光重合性組成物
JPH07159983A (ja) 1993-12-03 1995-06-23 Fuji Photo Film Co Ltd 感光性印刷版
JPH0854735A (ja) 1994-08-15 1996-02-27 Fuji Photo Film Co Ltd 光重合性組成物
JPH08224982A (ja) 1995-02-22 1996-09-03 Konica Corp 転写箔及びそれを用いたｉｄカード
JPH08324137A (ja) 1996-07-01 1996-12-10 Konica Corp 画像記録体およびその製造方法
JPH08325991A (ja) 1995-05-22 1996-12-10 New Oji Paper Co Ltd 両面キャストコート紙の製造方法
JPH09134011A (ja) 1995-09-08 1997-05-20 Konica Corp 感光性組成物、感光性平版印刷版及びそれを用いた画像形成方法
JPH10863A (ja) 1996-06-12 1998-01-06 Konica Corp 熱転写シート及びそれを用いて形成した画像要素
JPH1030012A (ja) 1996-04-19 1998-02-03 Dainippon Ink & Chem Inc 活性エネルギ−線硬化型樹脂組成物及び被覆材
JP2791143B2 (ja) 1988-11-08 1998-08-27 サイカラー・インコーポレーテッド 遷移金属配立錯体カチオンとボレートアニオンを含有した感光性組成物及びそれを使用した感光性材料
JPH11350398A (ja) 1998-06-15 1999-12-21 Kyowa Rami Coat:Kk 紙面のコーティング方法およびコーティング装置
JP2000313850A (ja) 1999-04-28 2000-11-14 Toyo Ink Mfg Co Ltd ゲルワニスおよび活性エネルギー線硬化性被覆組成物
JP2001031892A (ja) 1999-07-23 2001-02-06 Toyo Ink Mfg Co Ltd 紫外線硬化型塗料組成物及びその利用
JP2001040068A (ja) 1999-07-27 2001-02-13 Asahi Denka Kogyo Kk 光重合性組成物
JP2001049200A (ja) 1999-08-11 2001-02-20 Soken Chem & Eng Co Ltd アクリル系粘着剤組成物、該組成物を用いた粘着テープの製造方法および粘着テープ
JP2001055507A (ja) 1999-08-19 2001-02-27 Kansai Paint Co Ltd 活性エネルギー線硬化性組成物およびその被膜形成方法
JP2001133969A (ja) 1999-11-01 2001-05-18 Fuji Photo Film Co Ltd ネガ型平版印刷版原版
JP2001220526A (ja) 2000-02-09 2001-08-14 Brother Ind Ltd インクジェット記録方式用エネルギー線硬化型組成物
JP2001310937A (ja) 2000-04-27 2001-11-06 Hitachi Chem Co Ltd 硬化性オキセタン組成物およびその硬化方法ならびにその方法により得られる硬化物
JP2001310938A (ja) 2000-04-28 2001-11-06 Showa Denko Kk 重合性組成物、その硬化物と製造方法
JP2001343742A (ja) 2000-05-30 2001-12-14 Fuji Photo Film Co Ltd 感熱性組成物及びそれを用いた平版印刷版原版
JP2002006482A (ja) 2000-06-20 2002-01-09 Fuji Photo Film Co Ltd 感熱性組成物及びそれを用いた平版印刷版原版
JP2002116539A (ja) 2000-10-11 2002-04-19 Fuji Photo Film Co Ltd 平版印刷版原版
JP2002148790A (ja) 2000-09-04 2002-05-22 Fuji Photo Film Co Ltd 感熱性組成物、それを用いた平版印刷版原版及びスルホニウム塩化合物
JP2003026711A (ja) 2001-07-16 2003-01-29 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化性組成物、およびそれを用いてなるオーバープリント用ニス、その塗工物
JP2004102031A (ja) 2002-09-11 2004-04-02 Fuji Photo Film Co Ltd 重合性組成物及びそれを用いた平版印刷版原版
JP2004189695A (ja) 2002-12-13 2004-07-08 National Institute Of Advanced Industrial & Technology クロマノン類またはチオクロマノン類の製造方法
JP2005036152A (ja) 2003-07-18 2005-02-10 Toyo Ink Mfg Co Ltd 紫外線硬化型塗料組成物及びその被塗物
JP2005314832A (ja) 2004-04-28 2005-11-10 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化性脱墨用オーバーコートニス、その印刷物、印刷物の再生方法。
JP2005314511A (ja) 2004-04-28 2005-11-10 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化性脱墨用オーバーコートニス、その印刷物、印刷物の再生方法。
JP2006297690A (ja) 2005-04-19 2006-11-02 Mitsubishi Heavy Ind Ltd 枚葉印刷機の乾燥装置
JP4277936B1 (ja) 2008-12-05 2009-06-10 東洋インキ製造株式会社 活性エネルギー線硬化性組成物
JP2009208463A (ja) 2008-02-06 2009-09-17 Ryobi Ltd 印刷機の印刷方法及び印刷機
JP2009221441A (ja) 2008-03-19 2009-10-01 Toyo Ink Mfg Co Ltd 光硬化型インキ
JP4722326B2 (ja) 2001-05-28 2011-07-13 富士重工業株式会社 サブフレーム支持構造
JP4723664B2 (ja) 2009-08-17 2011-07-13 株式会社エフカム 導電パターン検査装置及び検査方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2658935A1 (de) * 1976-12-24 1978-07-06 Basf Ag Photopolymerisierbare masse und deren verwendung
ES2224893B1 (es) * 2004-08-04 2005-12-16 Neopack, S.L. Metodo y aparato para la obtencion de hologramas y/o efectos opticos sobre un material laminar.
EP2084005B1 (de) * 2006-11-21 2012-06-13 Basf Se Vorrichtung und verfahren zur herstellung eines sicherheitsproduktes
JP5457636B2 (ja) * 2008-01-22 2014-04-02 富士フイルム株式会社 光硬化性組成物、光硬化性インク組成物、光硬化物の製造方法、及び、インクジェット記録方法
US9624171B2 (en) * 2008-06-06 2017-04-18 Basf Se Photoinitiator mixtures
US8378002B2 (en) * 2008-07-16 2013-02-19 Fujifilm Corporation Aqueous ink composition, aqueous ink composition for inkjet recording, and inkjet recording method
JP2010024277A (ja) * 2008-07-16 2010-02-04 Fujifilm Corp インクジェット用インク組成物、及び、インクジェット記録方法

Patent Citations (106)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4420189B1 (de) 1965-06-03 1969-08-30
JPS4537377B1 (de) 1965-06-03 1970-11-27
US3567453A (en) 1967-12-26 1971-03-02 Eastman Kodak Co Light sensitive compositions for photoresists and lithography
JPS4842965B1 (de) 1968-04-02 1973-12-15
JPS476416B1 (de) 1968-04-16 1972-02-23
JPS473981B1 (de) 1968-06-11 1972-02-03
JPS4642363B1 (de) 1968-10-09 1971-12-15
GB1388492A (en) 1971-09-03 1975-03-26 Minnesota Mining & Mfg Chromophore-substituted halomethyl-s-triazines
JPS5534414B2 (de) 1972-06-02 1980-09-06
JPS5182102A (en) 1974-12-10 1976-07-19 Basf Ag Insatsuinki oyobi hifukuzairyonotameno hikarijugokanonaketsugozai
JPS53702A (en) 1975-12-23 1978-01-06 Dynachem Corp Adhesion promoting agent for polymerized film
JPS52134692A (en) 1976-05-04 1977-11-11 Fuji Photo Film Co Ltd Photopolymerizable composition
JPS53133428A (en) 1977-04-25 1978-11-21 Hoechst Ag Radiation sensitive copying constitute
JPS6026403B2 (ja) 1977-05-17 1985-06-24 メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング 不飽和化合物の光重合用光増感剤
US4318791A (en) 1977-12-22 1982-03-09 Ciba-Geigy Corporation Use of aromatic-aliphatic ketones as photo sensitizers
JPS579053B2 (de) 1978-01-09 1982-02-19
JPS6340799B2 (de) 1978-07-14 1988-08-12 Basf Ag
JPS55500806A (de) 1978-10-19 1980-10-16
JPS626223B2 (de) 1979-03-06 1987-02-09 Fuji Photo Film Co Ltd
JPS5637398A (en) 1979-09-03 1981-04-11 Takashi Murase Method and apparatus for polishing paper surface
JPS5675643A (en) 1979-11-07 1981-06-22 Hoechst Ag Photopolymerizable mixture and photopolymerizable copying material using same
US4343891A (en) 1980-05-23 1982-08-10 Minnesota Mining And Manufacturing Company Fixing of tetra (hydrocarbyl) borate salt imaging systems
JPS5730704A (en) 1980-06-24 1982-02-19 Bayer Ag Photopolymerizable mixture containing aroylphosphoric acid ester as photoinitiator
JPS6314340B2 (de) 1980-09-17 1988-03-30 Fuji Photo Film Co Ltd
EP0109773A2 (de) 1982-10-25 1984-05-30 Minnesota Mining And Manufacturing Company Dispersionsaufzeichnungsmaterialien mit Tetra(hydrocarbyl)-Boratsalzen
EP0109772A2 (de) 1982-10-25 1984-05-30 Minnesota Mining And Manufacturing Company Fixierung von Aufzeichnungsmaterialien mit Tetra(hydrocarbyl)-Boratsalzen
JPS59138205A (ja) 1983-01-20 1984-08-08 チバ−ガイギ−　アクチエンゲゼルシヤフト 被覆組成物およびその硬化方法
JPS59152396A (ja) 1983-02-11 1984-08-31 チバ−ガイギ−　アクチエンゲゼルシヤフト メタロセン，その製造方法およびメタロセンを含む光重合性組成物
JPS59174831A (ja) 1983-03-24 1984-10-03 Fuji Photo Film Co Ltd 光重合性組成物
JPS6084305A (ja) 1983-08-30 1985-05-13 バスフ　アクチェン　ゲゼルシャフト 光重合可能な混合物
DE3337024A1 (de) 1983-10-12 1985-04-25 Hoechst Ag, 6230 Frankfurt Lichtempfindliche, trichlormethylgruppen aufweisende verbindungen, verfahren zu ihrer herstellung und diese verbindungen enthaltendes lichtempfindliches gemisch
JPS61151197A (ja) 1984-12-20 1986-07-09 チバ‐ガイギー　アーゲー チタノセン類およびこれらのチタノセン類を含有する照射重合開始剤
JPH0731399B2 (ja) 1984-12-21 1995-04-10 三菱化学株式会社 光重合性組成物
JPS61194062A (ja) 1985-02-21 1986-08-28 メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング チオ置換ケトン化合物を用いる光重合開始剤
JPS6218537A (ja) 1985-07-16 1987-01-27 ザ・ミ−ド・コ−ポレ−シヨン 共開始剤として第三アミンを含有する感光性マイクロカプセルを用いた造像材料
JPS6258241A (ja) 1985-09-09 1987-03-13 Fuji Photo Film Co Ltd 感光性組成物
JPS6281345A (ja) 1985-09-28 1987-04-14 チバ―ガイギー　アクチェンゲゼルシャフト 共重合性光開始剤
JPS62135826A (ja) 1985-12-09 1987-06-18 Konishiroku Photo Ind Co Ltd 熱現像感光材料
JPS62173463A (ja) 1986-01-28 1987-07-30 Fuji Photo Film Co Ltd 画像形成方法
JPS62183457A (ja) 1986-02-07 1987-08-11 Fuji Photo Film Co Ltd 画像形成方法
JPS6341484A (ja) 1986-08-01 1988-02-22 チバ−ガイギ−　ア−ゲ− チタノセン、それらの製造法およびそれらを含有する組成物
JPS63143537A (ja) 1986-11-21 1988-06-15 イーストマン　コダック　カンパニー ネガ型フォトレジスト
JPS63142346A (ja) 1986-11-21 1988-06-14 イーストマン　コダック　カンパニー ネガ形フォトレジスト
JPS63142345A (ja) 1986-11-21 1988-06-14 イーストマン　コダック　カンパニー アジニウム活性化剤を含む画像高形成性組成物
JPS63138345A (ja) 1986-11-21 1988-06-10 イーストマン　コダック　カンパニー 写真像形成性システム
EP0284561A2 (de) 1987-03-26 1988-09-28 Ciba-Geigy Ag Neue alpha-Aminoacetophenone als Photoinitiatoren
JPS63278847A (ja) 1987-05-12 1988-11-16 Hamamatsu Seisakusho:Kk 枚葉印刷紙面の艶出し装置
JPS6433104A (en) 1987-06-25 1989-02-03 Ciba Geigy Ag Photopolymerizable composition
JPS6429997A (en) 1987-07-25 1989-01-31 Nittan Co Ltd Environmental abnormality alarming facility
JPS6434242A (en) 1987-07-30 1989-02-03 Idemitsu Kosan Co Material for preserving freshness of food
JPH0626483B2 (ja) 1987-09-14 1994-04-13 セイレイ工業株式会社 超音波センサーを用いた耕深制御装置
JPH0195788A (ja) 1987-10-08 1989-04-13 Chisso Corp ラットＮＡＤＨ−チトクロムｂ↓５環元酵素ゲノムＤＮＡ
JPH02249A (ja) 1987-12-01 1990-01-05 Ciba Geigy Ag チタノセンおよびそれを含有する光重合性組成物
JPH01152109A (ja) 1987-12-09 1989-06-14 Toray Ind Inc 光重合性組成物
JPH024705A (ja) 1988-03-24 1990-01-09 Dentsply Internatl Inc 光硬化性組成物用チタナート開始剤
JPH01304453A (ja) 1988-06-02 1989-12-08 Toyobo Co Ltd 光重合性組成物
JP2791143B2 (ja) 1988-11-08 1998-08-27 サイカラー・インコーポレーテッド 遷移金属配立錯体カチオンとボレートアニオンを含有した感光性組成物及びそれを使用した感光性材料
JPH02211452A (ja) 1988-12-01 1990-08-22 Polychrome Corp 光開始剤
JPH0431467A (ja) 1990-05-25 1992-02-03 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化性オーバーコートワニス
JPH0441563A (ja) 1990-06-08 1992-02-12 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化性オーバーコートワニス
JPH0441564A (ja) 1990-06-08 1992-02-12 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化性オーバーコートワニス
JPH059247A (ja) 1991-07-02 1993-01-19 Dainippon Ink & Chem Inc 活性エネルギー線硬化型樹脂組成物
JPH0529234A (ja) 1991-07-25 1993-02-05 Fujitsu Ltd エピタキシヤル成長法
JPH05142772A (ja) 1991-11-26 1993-06-11 Fuji Photo Film Co Ltd 光重合性組成物
JPH05263012A (ja) 1992-03-19 1993-10-12 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化性オーバーコートワニス
JPH05263013A (ja) 1992-03-19 1993-10-12 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化性オーバーコートワニス
JPH05281728A (ja) 1992-04-01 1993-10-29 Fuji Photo Film Co Ltd 光重合性組成物
JPH0643633A (ja) 1992-05-06 1994-02-18 Kyowa Hakko Kogyo Co Ltd 化学増幅型レジスト組成物
JPH068400A (ja) 1992-06-26 1994-01-18 Hamamatsu Seisakusho:Kk 紙面加工方法及びその装置
JPH069714A (ja) 1992-06-29 1994-01-18 Sumitomo Chem Co Ltd 光重合性組成物及び光制御板の製造方法
JPH06250387A (ja) 1993-03-01 1994-09-09 Sumitomo Chem Co Ltd キノンジアジドスルホン酸エステルの製法及び該製法により得られたキノンジアジドスルホン酸エステルを含有してなる感放射線性樹脂組成物
JPH06308727A (ja) 1993-04-19 1994-11-04 Fuji Photo Film Co Ltd 光重合性組成物
JPH07159983A (ja) 1993-12-03 1995-06-23 Fuji Photo Film Co Ltd 感光性印刷版
JPH0854735A (ja) 1994-08-15 1996-02-27 Fuji Photo Film Co Ltd 光重合性組成物
JPH08224982A (ja) 1995-02-22 1996-09-03 Konica Corp 転写箔及びそれを用いたｉｄカード
JPH08325991A (ja) 1995-05-22 1996-12-10 New Oji Paper Co Ltd 両面キャストコート紙の製造方法
JPH09134011A (ja) 1995-09-08 1997-05-20 Konica Corp 感光性組成物、感光性平版印刷版及びそれを用いた画像形成方法
JPH1030012A (ja) 1996-04-19 1998-02-03 Dainippon Ink & Chem Inc 活性エネルギ−線硬化型樹脂組成物及び被覆材
JPH10863A (ja) 1996-06-12 1998-01-06 Konica Corp 熱転写シート及びそれを用いて形成した画像要素
JPH08324137A (ja) 1996-07-01 1996-12-10 Konica Corp 画像記録体およびその製造方法
JPH11350398A (ja) 1998-06-15 1999-12-21 Kyowa Rami Coat:Kk 紙面のコーティング方法およびコーティング装置
JP2000313850A (ja) 1999-04-28 2000-11-14 Toyo Ink Mfg Co Ltd ゲルワニスおよび活性エネルギー線硬化性被覆組成物
JP2001031892A (ja) 1999-07-23 2001-02-06 Toyo Ink Mfg Co Ltd 紫外線硬化型塗料組成物及びその利用
JP2001040068A (ja) 1999-07-27 2001-02-13 Asahi Denka Kogyo Kk 光重合性組成物
JP2001049200A (ja) 1999-08-11 2001-02-20 Soken Chem & Eng Co Ltd アクリル系粘着剤組成物、該組成物を用いた粘着テープの製造方法および粘着テープ
JP2001055507A (ja) 1999-08-19 2001-02-27 Kansai Paint Co Ltd 活性エネルギー線硬化性組成物およびその被膜形成方法
JP2001133969A (ja) 1999-11-01 2001-05-18 Fuji Photo Film Co Ltd ネガ型平版印刷版原版
JP2001220526A (ja) 2000-02-09 2001-08-14 Brother Ind Ltd インクジェット記録方式用エネルギー線硬化型組成物
JP2001310937A (ja) 2000-04-27 2001-11-06 Hitachi Chem Co Ltd 硬化性オキセタン組成物およびその硬化方法ならびにその方法により得られる硬化物
JP2001310938A (ja) 2000-04-28 2001-11-06 Showa Denko Kk 重合性組成物、その硬化物と製造方法
JP2001343742A (ja) 2000-05-30 2001-12-14 Fuji Photo Film Co Ltd 感熱性組成物及びそれを用いた平版印刷版原版
JP2002006482A (ja) 2000-06-20 2002-01-09 Fuji Photo Film Co Ltd 感熱性組成物及びそれを用いた平版印刷版原版
JP2002148790A (ja) 2000-09-04 2002-05-22 Fuji Photo Film Co Ltd 感熱性組成物、それを用いた平版印刷版原版及びスルホニウム塩化合物
JP2002116539A (ja) 2000-10-11 2002-04-19 Fuji Photo Film Co Ltd 平版印刷版原版
JP4722326B2 (ja) 2001-05-28 2011-07-13 富士重工業株式会社 サブフレーム支持構造
JP2003026711A (ja) 2001-07-16 2003-01-29 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化性組成物、およびそれを用いてなるオーバープリント用ニス、その塗工物
JP2004102031A (ja) 2002-09-11 2004-04-02 Fuji Photo Film Co Ltd 重合性組成物及びそれを用いた平版印刷版原版
JP2004189695A (ja) 2002-12-13 2004-07-08 National Institute Of Advanced Industrial & Technology クロマノン類またはチオクロマノン類の製造方法
JP2005036152A (ja) 2003-07-18 2005-02-10 Toyo Ink Mfg Co Ltd 紫外線硬化型塗料組成物及びその被塗物
JP2005314832A (ja) 2004-04-28 2005-11-10 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化性脱墨用オーバーコートニス、その印刷物、印刷物の再生方法。
JP2005314511A (ja) 2004-04-28 2005-11-10 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化性脱墨用オーバーコートニス、その印刷物、印刷物の再生方法。
JP2006297690A (ja) 2005-04-19 2006-11-02 Mitsubishi Heavy Ind Ltd 枚葉印刷機の乾燥装置
JP2009208463A (ja) 2008-02-06 2009-09-17 Ryobi Ltd 印刷機の印刷方法及び印刷機
JP2009221441A (ja) 2008-03-19 2009-10-01 Toyo Ink Mfg Co Ltd 光硬化型インキ
JP4277936B1 (ja) 2008-12-05 2009-06-10 東洋インキ製造株式会社 活性エネルギー線硬化性組成物
JP4723664B2 (ja) 2009-08-17 2011-07-13 株式会社エフカム 導電パターン検査装置及び検査方法

Non-Patent Citations (12)

* Cited by examiner, † Cited by third party
Title
"Application and Market of UV.EB Curing Technology", 1989, CMC, pages: 79
"Crosslinking Agent Handbook", 1981, TAISEISHA
"Organic Materials for Imaging", 1993, BUNSHIN PUBLISHING CO., pages: 187 - 192
"Polyester Resin Handbook", 1988, THE NIKKAN KOGYO SHIMBUN LTD.
"UV-EB Curing Handbook", 1985, KOBUNSHI KANKOUKAI
J. ORG. CHEM., vol. 29, 1964, pages 1527
J. P. FOUASSIER, J. F. RABEK, RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY, 1993, pages 77 - 117
JOURNAL OF HETEROCYCLIC CHEMISTRY, vol. 7, no. 3, 1970, pages 511
JOURNAL OF ORGANIC CHEMISTRY, 1945, pages 893
JOURNAL OF ORGANIC CHEMISTRY, 1965, pages 4939
M. R. SANDER ET AL., JOURNAL OF POLYMER SOCIETY, vol. 10, 1972, pages 3173
TETRAHEDRON, vol. 49, 1993, pages 939

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WO2014063997A1 (en) 2012-10-22 2014-05-01 Lamberti Spa 3-ketocoumarines for led photocuring
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US9951034B2 (en) 2012-10-22 2018-04-24 Igm Resins Italia S.R.L. 3-ketocoumarines for LED photocuring
EP2920255A4 (de) * 2012-11-19 2016-07-20 Hewlett Packard Development Co Zusammensetzungen für dreidimensionales (3d) drucken
US10280299B2 (en) 2012-11-19 2019-05-07 Hewlett-Packard Development Company, L.P. Compositions for three-dimensional (3D) printing
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